KR101980515B1 - Method for manufacturing semiconductor device - Google Patents

Method for manufacturing semiconductor device Download PDF

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KR101980515B1
KR101980515B1 KR1020120052391A KR20120052391A KR101980515B1 KR 101980515 B1 KR101980515 B1 KR 101980515B1 KR 1020120052391 A KR1020120052391 A KR 1020120052391A KR 20120052391 A KR20120052391 A KR 20120052391A KR 101980515 B1 KR101980515 B1 KR 101980515B1
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film
oxide semiconductor
oxygen
semiconductor film
insulating film
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KR1020120052391A
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KR20120129795A (en
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주니치 고에주카
유헤이 사토
순페이 야마자키
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가부시키가이샤 한도오따이 에네루기 켄큐쇼
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
    • H01L29/78693—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate the semiconducting oxide being amorphous
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/04—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their crystalline structure, e.g. polycrystalline, cubic or particular orientation of crystalline planes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thin Film Transistor (AREA)
  • Solid State Image Pick-Up Elements (AREA)
  • Recrystallisation Techniques (AREA)
  • Metal-Oxide And Bipolar Metal-Oxide Semiconductor Integrated Circuits (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

An object of the present invention is to provide stable electrical characteristics to a semiconductor device using an oxide semiconductor and to achieve high reliability.
In the manufacturing process of a transistor including an oxide semiconductor film, an amorphous oxide semiconductor film is formed, and oxygen is introduced into the amorphous oxide semiconductor film to form an amorphous oxide semiconductor film containing excess oxygen. After forming an aluminum oxide film on the amorphous oxide semiconductor film, heat treatment is performed to crystallize at least a portion of the amorphous oxide semiconductor film to form a crystalline oxide semiconductor film.

Description

Manufacturing Method of Semiconductor Device {METHOD FOR MANUFACTURING SEMICONDUCTOR DEVICE}

A manufacturing method of a semiconductor device and a semiconductor device.

In addition, in this specification, a semiconductor device refers to the general apparatus which can function by using a semiconductor characteristic, and an electro-optical device, a semiconductor circuit, and an electronic device are all semiconductor devices.

A technique for constructing a transistor (also referred to as a thin film transistor (TFT)) using a semiconductor thin film formed on a substrate having an insulating surface has attracted attention. The transistor is widely applied to electronic devices such as integrated circuits (ICs) and image display devices (display devices). Although silicon-based semiconductor materials are widely known as semiconductor thin films applicable to transistors, oxide semiconductors have attracted attention as other materials.

For example, a transistor using an amorphous oxide containing indium (In), gallium (Ga), and zinc (Zn) having an electron carrier concentration of less than 10 18 / cm 3 is disclosed as an active layer of the transistor (see Patent Document 1). ).

Japanese Laid-Open Patent Publication No. 2006-165528

However, in the oxide semiconductor, the electrical conductivity changes when a difference from the stoichiometric composition, incorporation of hydrogen or water to form an electron donor, etc. occurs in the thin film forming step. This phenomenon becomes a factor of fluctuation of electrical characteristics in the transistor using the oxide semiconductor.

In view of these problems, it is an object of the present invention to provide stable electrical characteristics to a semiconductor device using an oxide semiconductor and to achieve high reliability.

In the manufacturing process of a transistor including an oxide semiconductor film, an amorphous oxide semiconductor film is formed, and oxygen is introduced into the amorphous oxide semiconductor film to form an amorphous oxide semiconductor film containing excess oxygen. After the aluminum oxide film is formed on the amorphous oxide semiconductor film, heat treatment is performed to crystallize at least a portion of the amorphous oxide semiconductor film to form an oxide semiconductor film (also referred to as a crystalline oxide semiconductor film) containing crystals.

As a method of introducing oxygen (including at least one of oxygen radicals, oxygen atoms, and oxygen ions) into the amorphous oxide semiconductor film, an ion implantation method, an ion doping method, a plasma immersion ion implantation method, a plasma treatment, or the like can be used.

The crystalline oxide semiconductor film is an oxide semiconductor film containing crystals and having crystallinity. The crystal state in the crystalline oxide semiconductor film may be in a disordered direction or in a state having a constant orientation.

In one embodiment of the invention disclosed in the present specification, oxygen is introduced and heat treatment is performed on an amorphous oxide semiconductor film covered with an aluminum oxide film to crystallize at least a portion of the amorphous oxide semiconductor film to form a c-axis that is approximately perpendicular to the surface. An oxide semiconductor film (crystalline oxide semiconductor film) containing crystals can be formed.

An oxide semiconductor film including crystals having a c-axis that is approximately perpendicular to the surface is not a single crystal structure, but is also an amorphous structure, and also has a c-axis alignment (C Axis Aligned Crystalline Oxide Semiconductor; CAAC-OS). It is a film.

CAAC-OS has a c-axis orientation and has a triangular or hexagonal atomic arrangement when viewed in the direction of the ab plane, surface, or interface, and in the c-axis, the metal atoms are layered or the metal atoms and oxygen atoms are arranged in layers. In the ab plane (or surface or interface), an oxide semiconductor containing crystals (rotated about the c axis) in which the a-axis or b-axis directions are different.

Broadly speaking, CAAC-OS is a non-single crystal, which has a triangular or hexagonal, equilateral triangle or equilateral hexagonal arrangement when viewed in a direction perpendicular to its ab plane, and is a metal when viewed in a direction perpendicular to the c-axis direction. It refers to a material containing a valence layered or a phase in which metal atoms and oxygen atoms are arranged in layers.

Although CAAC-OS is not a single crystal, it is not formed by only amorphous. In addition, although the CAAC-OS includes a crystallized portion (crystal portion), in some cases, the boundary between one crystal portion and another crystal portion cannot be clearly determined.

Part of the oxygen constituting the CAAC-OS may be replaced with nitrogen. In addition, the c-axis of the individual crystal parts constituting the CAAC-OS may be aligned in a predetermined direction (for example, a direction perpendicular to the surface of the substrate on which the CAAC-OS film is formed, the surface of the CAAC-OS film, the film surface, the interface, or the like). . Alternatively, the normal line of the ab planes of the individual crystal parts constituting the CAAC-OS may face a certain direction (for example, a direction perpendicular to the substrate plane, the surface, the membrane plane, the interface, and the like).

By setting it as the said crystalline oxide semiconductor film, the change of the electrical characteristic of a transistor by irradiation of visible light or an ultraviolet light can be suppressed more, and it can be set as a highly reliable semiconductor device.

By the oxygen introduction step, the oxide semiconductor film (amorphous oxide semiconductor film and crystalline oxide semiconductor film) includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. In this case, the content of oxygen is such that it exceeds the stoichiometric composition ratio of the oxide semiconductor. Alternatively, the content of oxygen is such that it exceeds the amount of oxygen in the case of a single crystal. Oxygen may exist between the lattice of an oxide semiconductor. The composition of such an oxide semiconductor can be expressed as InGaZn m O m + 3x (x> 1). For example, when m = 1, the composition of the oxide semiconductor is InGaZnO 1 + 3x (x> 1), and in the case of excess oxygen, 1 + 3x represents a value exceeding 4.

In the oxide semiconductor film, oxygen vacancies exist at a place where oxygen is released. An oxide semiconductor which does not contain oxygen excessively cannot supplement the deficiency with other oxygen even if an oxygen deficiency occurs. However, the crystalline oxide semiconductor film of one embodiment of the disclosed invention is a crystalline oxide semiconductor film (for example, a CAAC-OS film) containing excessive oxygen, and the crystalline oxide semiconductor film is said to have an oxygen deficiency. Even if the film contains excess oxygen (preferably more than stoichiometric composition ratio) in the film, the excess oxygen acts on the defective portion and the oxygen can be immediately replenished with the defective portion.

The aluminum oxide film formed on the oxide semiconductor film has a high blocking effect (block effect) that does not transmit the film to both impurities such as hydrogen, moisture, hydroxyl groups, or hydrides (also called hydrogen compounds) and oxygen.

Therefore, the aluminum oxide film prevents the incorporation of impurities, such as hydrogen and moisture, into the oxide semiconductor film during the production process and after the production, and the release of oxygen from the oxide semiconductor film as the main component material constituting the oxide semiconductor. It functions as a protective film to prevent.

In addition, since the heat treatment for crystallizing the amorphous oxide semiconductor film is performed in a state where the amorphous oxide semiconductor film is covered with the aluminum oxide film, oxygen can be prevented from being released from the amorphous oxide semiconductor film by the heat treatment for crystallization. Therefore, the obtained crystalline oxide semiconductor film can hold | maintain the amount of oxygen which an amorphous oxide semiconductor film contains, and it can be set as the film | membrane containing the area | region which oxygen content is excessive with respect to the stoichiometric composition ratio in an oxide semiconductor crystal state.

Therefore, the crystalline oxide semiconductor film formed is of high purity because the incorporation of impurities such as hydrogen and moisture and the release of excess oxygen are prevented by the aluminum oxide film, and thus the oxide semiconductor is stoichiometric in the crystal state. It includes the region in which the content of oxygen is excessive with respect to the composition ratio.

Therefore, by using the crystalline oxide semiconductor film in the transistor, it is possible to reduce the deviation of the threshold voltage V th and the shift ΔVth of the threshold voltage due to the oxygen deficiency.

In addition, before the aluminum oxide film is formed, it is preferable to perform dehydration or dehydrogenation treatment by a heat treatment in which the amorphous oxide semiconductor film is intentionally excluded from the oxide semiconductor film with impurities such as impurities containing hydrogen atoms or hydrogen atoms such as water. Do.

By removing hydrogen from the oxide semiconductor, making it highly purified so as not to contain impurities as much as possible, and supplementing the oxygen deficiency, an oxide semiconductor of type I (intrinsic) or an oxide semiconductor very close to type I (intrinsic) can be obtained. In other words, by removing impurities such as hydrogen and water as much as possible and replenishing the oxygen deficiency, the type I (intrinsic semiconductor) which is highly purified can be made close to it. By doing in this way, the Fermi level Ef of an oxide semiconductor can be made to the same level as the intrinsic Fermi level Ei.

One embodiment of the configuration of the invention disclosed in this specification forms an insulating film, an aluminum oxide film, an amorphous oxide semiconductor film interposed between the insulating film and the aluminum oxide film, and heat-processes the amorphous oxide semiconductor film. At least a part of the crystals are crystallized to form an oxide semiconductor film containing crystals, and the amorphous oxide semiconductor film includes a region in which oxygen content is excessive with respect to the stoichiometric composition ratio of the oxide semiconductor in the crystal state. It is a manufacturing method of a semiconductor device.

One embodiment of the structure of the invention disclosed in this specification forms an insulating film, forms an amorphous oxide semiconductor film on the said insulating film, injects oxygen into the said amorphous oxide semiconductor film, and oxidizes on the amorphous oxide semiconductor film which injected the said oxygen. An oxide film is formed, the oxide oxide film injected with oxygen is subjected to heat treatment to crystallize at least a portion thereof to form an oxide semiconductor film containing crystals, and the oxide semiconductor is crystallized in the amorphous oxide semiconductor film injected with oxygen. It is the manufacturing method of the semiconductor device in which the area | region with excess oxygen content is contained with respect to the stoichiometric composition ratio in a state.

One embodiment of the configuration of the invention disclosed in this specification forms an insulating film, an amorphous oxide semiconductor film is formed on the insulating film, an aluminum oxide film is formed on the amorphous oxide semiconductor film, and passes through the aluminum oxide film to pass through the amorphous oxide semiconductor. Oxide is injected into the film, heat treatment is performed on the amorphous oxide semiconductor film into which the oxygen is injected, and at least a part thereof is crystallized to form an oxide semiconductor film containing crystals. The amorphous oxide semiconductor film into which the oxygen is injected is the oxide semiconductor. It is the manufacturing method of the semiconductor device in which the area | region with excess content of oxygen is contained with respect to the stoichiometric composition ratio in a temporary crystal state.

In one embodiment of the present invention, a semiconductor device having a transistor having various structures, such as a top gate structure, a bottom gate structure, a staggered type thereof, or a planar type, can be manufactured. In addition, in the step of introducing oxygen into the amorphous oxide semiconductor film, oxygen may be introduced directly into the exposed amorphous oxide semiconductor film, another film is formed on the amorphous oxide semiconductor film, and oxygen is passed through the film to the amorphous oxide semiconductor film. You may introduce. By the structure of the transistor, the step of introducing oxygen into the amorphous oxide semiconductor film in the manufacturing process of the semiconductor device is performed even if the exposed amorphous oxide semiconductor film is exposed to the insulating film (gate insulating film, insulating film (oxidation) on the amorphous oxide semiconductor film. Aluminum oxide film), or a gate insulating film and an insulating film (including an aluminum oxide film), or an amorphous oxide semiconductor film formed by laminating a gate insulating film and a gate electrode layer.

In the above configuration, the oxide semiconductor film containing the crystal obtained by crystallization by heat treatment is preferably a crystalline oxide semiconductor (CAAC-OS) film containing a crystal having a c-axis approximately perpendicular to the surface.

In the insulating film, the region where the amorphous oxide semiconductor film is in contact with each other is preferably a surface whose surface roughness is reduced. Specifically, the average surface roughness of the insulating film surface is preferably 1 nm or less, preferably 0.3 nm or less, and more preferably 0.1 nm or less. By forming the oxide semiconductor film on the surface of the insulating film having reduced surface roughness, an oxide semiconductor film having stable and good crystallinity can be obtained.

In the above structure, an oxide insulating film may be formed between the gate electrode layer and the aluminum oxide film. In addition, before forming the aluminum oxide film, a sidewall insulating layer having a sidewall structure covering the side surface of the gate electrode layer may be formed.

Moreover, in the said structure, you may heat-process to discharge | release hydrogen or water to the amorphous oxide semiconductor film before an oxygen introduction process and the formation process of an aluminum oxide film.

As described above, a transistor having a crystalline oxide semiconductor film that is highly purified and contains excessive oxygen to compensate for oxygen deficiency has an electrical characteristic variation suppressed and is electrically stable. Therefore, a highly reliable semiconductor device using an oxide semiconductor having stable electrical characteristics can be provided.

By forming the aluminum oxide film on the crystalline oxide semiconductor film so that excess oxygen contained in the oxide semiconductor film is not released by heat treatment, a defect is generated at the interface between the crystalline oxide semiconductor and the layers in contact with the upper and lower portions thereof, and the defect This can be prevented from increasing. That is, since the excess oxygen contained in the crystalline oxide semiconductor film acts to fill the oxygen vacancy defect, a highly reliable semiconductor device having stable electrical characteristics can be provided.

Therefore, one embodiment of the disclosed invention can manufacture a transistor having stable electrical characteristics.

Moreover, one aspect of the disclosed invention can manufacture a semiconductor device having good electrical characteristics and high reliability.

BRIEF DESCRIPTION OF THE DRAWINGS The figure explaining one form of the manufacturing method of a semiconductor device and a semiconductor device.
FIG. 2 A diagram for describing one embodiment of the method of manufacturing the semiconductor device and the semiconductor device. FIG.
3 A diagram for describing one embodiment of the method for manufacturing the semiconductor device and the semiconductor device.
4 A diagram for describing one embodiment of the method for manufacturing the semiconductor device and the semiconductor device.
FIG. 5 A diagram for describing one embodiment of the method of manufacturing the semiconductor device and the semiconductor device. FIG.
6 A diagram for describing one embodiment of the method for manufacturing the semiconductor device and the semiconductor device.
FIG. 7 A diagram for describing one embodiment of the method of manufacturing the semiconductor device and the semiconductor device. FIG.
8 is a diagram illustrating one embodiment of a method of manufacturing a semiconductor device and a semiconductor device.
9A to 9D illustrate one embodiment of a semiconductor device and a method for manufacturing the semiconductor device.
10 illustrates one embodiment of a semiconductor device.
11 illustrates one embodiment of a semiconductor device.
12 illustrates one embodiment of a semiconductor device.
13 illustrates one embodiment of a semiconductor device.
14 illustrates one embodiment of a semiconductor device.
15A to 15D illustrate one embodiment of a semiconductor device.
16 illustrates an electronic device.
17 is a diagram showing a SIMS measurement result of Comparative Example Sample A. FIG.
18 is a diagram showing a SIMS measurement result of Example Sample A.
19 shows TDS measurement results of Comparative Example Sample B. FIG.
20 shows TDS measurement results of Example Sample B. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention disclosed in this specification is described in detail using drawing. However, the invention disclosed in this specification is not limited to the following description, and it can be easily understood by those skilled in the art that the form and details can be variously changed. In addition, invention disclosed in this specification is not interpreted limited to the description content of embodiment shown below. In addition, the ordinal numbers attached as 1st and 2nd are used for convenience, and do not show a process order or lamination order. In addition, in this specification, as a matter for specifying invention, the original name is not shown.

(Embodiment 1)

In this embodiment, one embodiment of the semiconductor device and the manufacturing method of the semiconductor device will be described with reference to FIG. 1. In this embodiment, a transistor having an oxide semiconductor film is shown as an example of a semiconductor device.

The structure of the transistor is not particularly limited, and for example, a top gate structure or a staggered type and a planar type of a bottom gate structure can be used. The transistor may be a single gate structure in which one channel formation region is formed, a double gate structure in which two channels are formed, or a triple gate structure in which three transistors are formed. Alternatively, a dual gate type may be provided having two gate electrode layers disposed above and below the channel region via a gate insulating film.

As shown in FIG. 1E, the transistor 410 includes a gate electrode layer 401, a gate insulating film 402, a crystalline oxide semiconductor film 403, and a source electrode layer 405a on a substrate 400 having an insulating surface. And a drain electrode layer 405b. An insulating film 407 is formed over the transistor 410.

In addition, although the insulating film 407 may be a single layer or lamination, it is set as the structure containing an aluminum oxide film. In this embodiment, the gate insulating film 402 is a silicon oxide film, and the insulating film 407 is an aluminum oxide film.

The crystalline oxide semiconductor film 403 is a crystalline oxide semiconductor film containing crystals. The crystalline oxide semiconductor film 403 is an oxide semiconductor film containing crystals having an ab plane parallel to the surface and having a c-axis approximately perpendicular to the surface. The crystalline oxide semiconductor film 403 is not a single crystal structure and is not an amorphous structure. is preferably a crystalline oxide semiconductor (CAAC-OS) having a c-axis orientation. By using the crystalline oxide semiconductor film, a change in the electrical characteristics of the transistor 410 caused by irradiation of visible light or ultraviolet light can be further suppressed, and a highly reliable semiconductor device can be obtained.

1A to 1E show an example of a method of manufacturing the transistor 410.

First, after the conductive film is formed on the substrate 400 having the insulating surface, the gate electrode layer 401 is formed by the first photolithography process. Moreover, you may form a resist mask by the inkjet method. When the resist mask is formed by the inkjet method, the photomask is not used, and thus manufacturing cost can be reduced.

Although there is no big restriction | limiting in the board | substrate which can be used for the board | substrate 400 which has an insulating surface, it is necessary to have heat resistance at least enough to endure later heat processing. For example, glass substrates, such as barium borosilicate glass and alumino borosilicate glass, a ceramic substrate, a quartz substrate, a sapphire substrate, etc. can be used. In addition, a single crystal semiconductor substrate such as silicon or silicon carbide, a polycrystalline semiconductor substrate, a compound semiconductor substrate such as silicon germanium, an SOI substrate, or the like may be used, or a semiconductor element formed on these substrates may be used as the substrate 400. .

As the substrate 400, a semiconductor device may be produced using a flexible substrate. In order to manufacture a flexible semiconductor device, the transistor 410 including the crystalline oxide semiconductor film 403 may be directly fabricated on the flexible substrate, or the crystalline oxide semiconductor film 403 is included in another fabrication substrate. The transistor 410 may be fabricated, and then peeled and transferred to a flexible substrate. In addition, in order to peel and transfer from a fabrication board | substrate to a flexible board | substrate, a peeling layer may be formed between a fabrication board | substrate and the transistor containing an oxide semiconductor film.

An insulating film serving as a base film may be formed between the substrate 400 and the gate electrode layer 401. The underlying film has a function of preventing diffusion of impurity elements from the substrate 400, and has a laminated structure of one or more films selected from a silicon nitride film, a silicon oxide film, a silicon nitride oxide film, or a silicon oxynitride film. It can form by.

As the material of the gate electrode layer 401, a metal material such as molybdenum, titanium, tantalum, tungsten, aluminum, copper, neodymium, scandium, or an alloy material containing these as a main component is used by plasma CVD or sputtering. It can be formed by single layer or lamination.

The material of the gate electrode layer 401 is indium tin oxide, indium oxide containing tungsten oxide, indium zinc oxide containing tungsten oxide, indium oxide containing titanium oxide, indium tin oxide containing titanium oxide, and indium. Nitrides of a conductive material having light transmissivity, such as indium tin oxide added with zinc oxide and silicon oxide, and a conductive material having light transmissivity may also be used. Moreover, it is good also as a laminated structure of the said translucent electroconductive material and the said metal material.

In addition, the gate electrode layer 401 has a laminated structure, and as one layer thereof, an In—Sn—O system, an In—Sn—Zn—O system, an In—Al—Zn—O system, Sn—Ga—Zn—O , Al-Ga-Zn-O, Sn-Al-Zn-O, In-Zn-O, Sn-Zn-O, Al-Zn-O, In-O, Sn-O Or a Zn-O-based metal oxide may be used. It is preferable to use the gate electrode layer 401 as a laminated structure and to use an oxynitride film (also referred to as an IGZON film) containing indium, gallium, and zinc, which are materials having a large work function, as one layer. An oxynitride film containing indium, gallium, and zinc is obtained by forming a film under a mixed gas atmosphere of argon and nitrogen.

For example, as the gate electrode layer 401, a laminated structure of a copper film, a tungsten film, an oxynitride film (IGZON film) containing indium, gallium, and zinc from the substrate 400 side, a tungsten film, and nitride A laminated structure of a tungsten film, a copper film, and a titanium film can be used.

Next, the gate insulating film 402 is formed on the gate electrode layer 401 by plasma CVD, sputtering, or the like. As the material of the gate insulating film 402, a silicon oxide film, a gallium oxide film, an aluminum oxide film, a silicon nitride film, a silicon oxynitride film, an aluminum oxynitride film, or a silicon nitride oxide film can be formed.

In addition, hafnium oxide, yttrium oxide, and hafnium silicate (HfSi x O y (x> 0, y> 0)) and hafnium silicate (HfSiO x N y (x> 0, The gate leakage current can be reduced by using high-k materials such as y> 0)), hafnium aluminate (HfAl x O y (x> 0, y> 0)), and lanthanum oxide.

Although the gate insulating film 402 may be a single layer or lamination, an oxide insulating film is preferable as a film which contacts the crystalline oxide semiconductor film 403. In this embodiment, a silicon oxide film is used as the gate insulating film 402.

Since the gate insulating film 402 is in contact with the crystalline oxide semiconductor film 403, it is preferable to have oxygen in an amount exceeding at least the stoichiometric ratio in the film (in the bulk). The region in which the oxygen content is excessive (excessive oxygen region) may be present in a part of the gate insulating film 402 (including an interface). For example, when a silicon oxide film is used as the gate insulating film 402, it is referred to as SiO 2 + α (where α> 0).

By making the silicon oxide film in contact with the crystalline oxide semiconductor film 403 contain a large amount of oxygen, it can function suitably as a supply source for supplying oxygen to the oxide semiconductor film.

Therefore, by using the gate insulating film 402, oxygen can be supplied to the crystalline oxide semiconductor film 403, so that the characteristics can be improved. By supplying oxygen to the crystalline oxide semiconductor film 403, the oxygen deficiency in the film can be compensated for.

A gate insulating film 402 containing a large amount (or excess) of oxygen, which is a source of oxygen, is formed in contact with the crystalline oxide semiconductor film 403 to thereby form oxygen from the gate insulating film 402 to the crystalline oxide semiconductor film 403. Can be supplied. For example, oxygen can be supplied to the crystalline oxide semiconductor film 403 by performing a heating step in a state where at least part of the crystalline oxide semiconductor film 403 and the gate insulating film 402 are in contact with each other.

In order to prevent hydrogen, hydroxyl groups, and moisture from being contained in the oxide insulating film formed on the gate insulating film 402 and the gate insulating film 402 as much as possible, as a pretreatment for film formation of the oxide semiconductor film, the gate is formed in the preheating chamber of the sputtering apparatus. It is preferable to preheat the substrate 400 on which the electrode layer 401 is formed or the substrate 400 on which the gate insulating film 402 is formed, and to remove and exhaust impurities such as hydrogen and moisture adsorbed on the substrate 400. . In addition, a cryopump is preferable for the exhaust means formed in the preheating chamber. In addition, the process of this preheating can also be abbreviate | omitted. This preheating may be similarly performed on the substrate 400 formed up to the source electrode layer 405a and the drain electrode layer 405b before the film formation of the insulating film 407.

Also, before forming the amorphous oxide semiconductor film 491 by the sputtering method, a powdery substance (particles, dust, etc.) adhered to the surface of the gate insulating film 402 by reverse sputtering which introduces argon gas to generate plasma. Is preferably removed. Reverse sputtering is a method of modifying a surface by applying a voltage using an RF power supply to a substrate side in an argon atmosphere without applying a voltage to the target side, thereby forming a plasma in the vicinity of the substrate. In addition, nitrogen, helium, oxygen, or the like may be used instead of the argon atmosphere.

Subsequently, an amorphous oxide semiconductor film 491 having a thickness of 2 nm or more and 200 nm or less, preferably 5 nm or more and 30 nm or less is formed on the gate insulating film 402 (see FIG. 1A).

As the method for forming the amorphous oxide semiconductor film 491, a sputtering method, a molecular beam epitaxy (MBE) method, a CVD method, a pulse laser deposition method, an ALD (Atomic Layer Deposition) method, or the like can be appropriately used. In addition, the amorphous oxide semiconductor film 491 may be formed using a sputtering apparatus for forming a film in a state in which a plurality of substrate surfaces are set substantially perpendicular to the sputtering target surface, a so-called CP sputtering system (Columner Plasma Sputtering system). good.

As an oxide semiconductor used for the amorphous oxide semiconductor film 491, it is preferable to contain at least indium (In) or zinc (Zn). It is particularly preferable to contain In and Zn. Moreover, as a stabilizer for reducing the dispersion | variation in the electrical characteristics of the transistor using the said oxide semiconductor, it is preferable to have gallium (Ga) besides these. It is also preferable to have tin (Sn) as the stabilizer. Moreover, it is preferable to have hafnium (Hf) as a stabilizer. Moreover, it is preferable to have aluminum (Al) as a stabilizer.

In addition, as other stabilizers, lanthanoids, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb) Or any one or more of dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

For example, indium oxide, tin oxide, zinc oxide, In-Zn oxide, Sn-Zn oxide, Al-Zn oxide, Zn-Mg oxide, Sn-Mg which are oxides of binary metals as oxide semiconductors In-Ga-Zn oxide (also referred to as IGZO), In-Al-Zn oxide, In-Sn-Zn oxide , Sn-Ga-Zn oxide, Al-Ga-Zn oxide, Sn-Al-Zn oxide, In-Hf-Zn oxide, In-La-Zn oxide, In-Ce-Zn oxide, In -Pr-Zn oxide, In-Nd-Zn oxide, In-Sm-Zn oxide, In-Eu-Zn oxide, In-Gd-Zn oxide, In-Tb-Zn oxide, In-Dy -Zn oxide, In-Ho-Zn oxide, In-Er-Zn oxide, In-Tm-Zn oxide, In-Yb-Zn oxide, In-Lu-Zn oxide, quaternary metal oxide Phosphorus In-Sn-Ga-Zn-based oxide, In-Hf-Ga-Zn-based oxide, In-Al-Ga-Zn-based oxide, In-Sn-Al-Zn-based oxide, In-Sn-Hf-Zn-based oxide , In-Hf-Al-Zn-based oxides can be used have.

Here, for example, an In—Ga—Zn-based oxide means an oxide having In, Ga, and Zn as main components, and the ratio of In, Ga, and Zn does not matter. In addition, metallic elements other than In, Ga, and Zn may be contained.

As the oxide semiconductor, a material represented by InMO 3 (ZnO) m (m> 0, and m is not an integer) may be used. M represents one metal element or a plurality of metal elements selected from Ga, Fe, Mn and Co. As the oxide semiconductor, a material represented by In 2 SnO 5 (ZnO) n (n> 0, and n is an integer) may be used.

For example, In: Ga: Zn = 1: 1: 1 (= 1/3: 1/3: 1/3) or In: Ga: Zn = 2: 2: 1 (= 2/5: 2/5 In-Ga-Zn-based oxides having an atomic ratio of: 1/5) and oxides near the composition can be used. Or In: Sn: Zn = 1: 1: 1 (= 1/3: 1/3: 1/3), In: Sn: Zn = 2: 1: 3 (= 1/3: 1/6: 1 / 2) or an In-Sn-Zn-based oxide having an atomic ratio of In: Sn: Zn = 2: 1: 5 (= 1/4: 1/8: 5/8) or an oxide near its composition may be used. .

However, the present invention is not limited to these, and those having an appropriate composition may be used in accordance with required semiconductor characteristics (mobility, threshold value, deviation, and the like). Moreover, in order to acquire the required semiconductor characteristic, it is preferable to make carrier density | concentration, impurity concentration, defect density, the atomic ratio of a metal element and oxygen, the bond distance between atoms, density, etc. as suitable.

For example, in In—Sn—Zn-based oxides, high mobility can be obtained relatively easily.

For example, the composition of the oxide whose atomic ratio of In, Ga, and Zn is In: Ga: Zn = a: b: c (a + b + c = 1) has an atomic ratio of In: Ga: Zn = In the vicinity of the composition of an oxide of A: B: C (A + B + C = 1), that a, b and c satisfy (aA) 2 + (bB) 2 + (cC) 2 ≤ r 2 . In other words, r may be, for example, 0.05. The same applies to other oxides.

In the crystalline oxide semiconductor film 403 which is an oxide semiconductor having crystallinity, defects in the bulk can be further reduced, and the mobility of the oxide semiconductor in an amorphous state can be obtained by increasing the flatness of the surface. In order to increase the flatness of the surface, it is preferable to form an oxide semiconductor on a flat surface, and specifically, the average surface roughness Ra is 1 nm or less, preferably 0.3 nm or less, more preferably 0.1 nm or less. It is good to form.

Ra is a three-dimensional extension of the centerline average roughness defined in JIS B0601 so that it can be applied to a plane, and can be expressed as a value obtained by averaging the absolute value of the deviation from the reference plane to the designated plane. It is defined as

Figure 112012039460267-pat00001

In the above, S 0 is surrounded by four points represented by the measurement surface (coordinates (x 1 , y 1 ) (x 1 , y 2 ) (x 2 , y 1 ) (x 2 , y 2 )). The area of a rectangular region), and Z 0 indicates the average height of the measurement surface. Ra can be evaluated by atomic force microscopy (AFM).

Therefore, the planarization process may be performed in the region where the crystalline oxide semiconductor film 403 (the amorphous oxide semiconductor film 491 in FIG. 1A) is formed in contact with the gate insulating film 402. Although it does not specifically limit as a planarization process, Polishing process (for example, a chemical mechanical polishing (CMP) method), a dry etching process, and a plasma process can be used.

As the plasma treatment, for example, reverse sputtering may be performed in which argon gas is introduced to generate plasma.

As the planarization treatment, the polishing treatment, the dry etching treatment and the plasma treatment may be performed a plurality of times, or a combination thereof may be performed. In addition, when performing in combination, process order is not specifically limited, either, According to the uneven | corrugated state of the surface of the gate insulating film 402, it is good to set suitably.

In this embodiment, an amorphous oxide semiconductor film 491 is formed by sputtering using an In—Ga—Zn-based metal oxide target. As the atmosphere for forming the amorphous oxide semiconductor film 491, it can be carried out under a rare gas (typically argon) atmosphere, under an oxygen atmosphere, or under a mixed atmosphere of the rare gas and oxygen.

In addition, the amorphous oxide semiconductor film 491 is formed under the conditions of containing a large amount of oxygen during film formation (for example, by forming a film by sputtering in an atmosphere of 100% oxygen) and containing a large amount of oxygen ( Preferably, the oxide semiconductor is preferably formed into a film containing an excess region of oxygen relative to the stoichiometric composition ratio in the crystal state.

As a target for producing an oxide semiconductor film by the sputtering method, for example, In-Ga is used as the composition ratio using an oxide target of In 2 O 3 : Ga 2 O 3 : ZnO = 1: 1: 2 [mol ratio]. -Form a Zn film. The present invention is not limited to the target material and the composition, e.g., In 2 O 3: Ga 2 O 3: ZnO = 1: 1: 1 [mol ratio] may be used in the metal oxide target.

Moreover, the filling rate of a metal oxide target is 90% or more and 100% or less, Preferably they are 95% or more and 99.9% or less. By using the metal oxide target with a high filling rate, the oxide semiconductor film formed into a film can be made into a dense film.

As a sputtering gas used for forming an oxide semiconductor film, it is preferable to use the high purity gas from which impurities, such as hydrogen, water, a hydroxyl group, or a hydride, were removed.

The substrate is held in the deposition chamber maintained at a reduced pressure. A sputtering gas from which hydrogen and moisture have been removed is introduced while removing residual moisture in the film formation chamber, and an amorphous oxide semiconductor film 491 is formed on the substrate 400 using the target. In order to remove residual moisture in the film formation chamber, it is preferable to use a vacuum pump of an adsorption type, for example, a cryopump, an ion pump, or a titanium servation pump. The exhaust means may be a cold trap applied to the turbomolecular pump. In the film formation chamber exhausted using a cryopump, for example, compounds containing hydrogen atoms such as hydrogen atoms and water (H 2 O) (more preferably, compounds containing carbon atoms) are exhausted. The concentration of impurities contained in the amorphous oxide semiconductor film 491 formed in the deposition chamber can be reduced.

In addition, the gate insulating film 402 and the amorphous oxide semiconductor film 491 are preferably formed continuously without releasing them into the atmosphere. If the gate insulating film 402 and the amorphous oxide semiconductor film 491 are formed continuously without exposing to the atmosphere, it is possible to prevent impurities such as hydrogen and moisture from adsorbing onto the surface of the gate insulating film 402.

The amorphous oxide semiconductor film 491 may be subjected to a heat treatment for removing (dehydrating or dehydrogenating) excess hydrogen (including water and hydroxyl groups). The temperature of the heat treatment is a temperature at which the amorphous oxide semiconductor film is not crystallized, and is typically 250 ° C. or more and 400 ° C. or less, preferably 300 ° C. or less.

In addition, when the heat treatment for dehydration or dehydrogenation is performed after the formation of the amorphous oxide semiconductor film 491 and before the step of introducing oxygen into the amorphous oxide semiconductor film 491, at any timing in the manufacturing process of the transistor 410. You may carry out.

In addition, if the heat treatment for dehydration or dehydrogenation is performed before the amorphous oxide semiconductor film 491 is processed into an island shape, the oxygen contained in the gate insulating film 402 can be prevented from being released by the heat treatment. It is preferable because of that.

Moreover, in heat processing, it is preferable that nitrogen, or rare gas, such as helium, neon, argon, does not contain water, hydrogen, etc. Alternatively, the purity of nitrogen introduced into the heat treatment apparatus, or rare gases such as helium, neon, and argon is 6N (99.9999%) or more, preferably 7N (99.99999%) or more (ie, impurity concentration is 1 ppm or less, preferably 0.1 ppm). It is preferable to set it as below).

In addition, after heating the amorphous oxide semiconductor film 491 by heat treatment, high purity oxygen gas, high purity oxygen dioxygen gas, or ultra-dry air (CRDS (cavity ring-down laser spectroscopy) dew point system in the same furnace) The water content in the case of measurement may introduce 20 ppm or less (-55 degreeC in conversion of dew point) or less, Preferably it is 1 ppm or less, Preferably it is 10 ppm or less of air. It is preferable that water, hydrogen, etc. are not contained in oxygen gas or oxygen dioxygen gas. Alternatively, the purity of the oxygen gas or the oxygen dioxygen gas introduced into the heat treatment apparatus is 6N or more, preferably 7N or more (that is, the impurity concentration in the oxygen gas or oxygen dioxygen gas is 1 ppm or less, preferably 0.1 ppm or less). desirable. The purity of the amorphous oxide semiconductor film is increased by supplying oxygen, which is a main component material of the amorphous oxide semiconductor, which has been simultaneously reduced by the action of oxygen gas or oxygen dioxygen gas, which has been simultaneously reduced by the process of removing impurities by dehydration or dehydrogenation. It can be electrically type I (intrinsic).

Next, oxygen 431 (including at least one of oxygen radicals, oxygen atoms, and oxygen ions) is introduced into the amorphous oxide semiconductor film 491, and oxygen is supplied to the amorphous oxide semiconductor film 491. . As the method for introducing oxygen, an ion implantation method, an ion doping method, a plasma immersion ion implantation method, a plasma treatment, or the like can be used.

In the manufacturing process of the transistor 410 in the present embodiment, the oxygen introduction step is performed after the amorphous oxide semiconductor film 491 is formed and before the aluminum oxide film is formed as the insulating film 407. In addition, the heat processing for dehydration or dehydrogenation is performed before oxygen introduction process. The oxygen introduction step may be introduced directly into the amorphous oxide semiconductor film, or may be introduced into the amorphous oxide semiconductor film through another film such as a gate insulating film or an insulating film. When oxygen is introduced into the amorphous oxide semiconductor film through another film, an ion implantation method, an ion doping method, a plasma immersion ion implantation method, or the like may be used. However, as in the present embodiment, oxygen is exposed to the exposed amorphous oxide semiconductor film 491. In the case of direct introduction, a plasma treatment or the like can also be used.

In this embodiment, oxygen 431 is injected into the amorphous oxide semiconductor film 491 by the ion implantation method. By the implantation process of oxygen 431, the amorphous oxide semiconductor film 491 has an amorphous oxide semiconductor film 441 in which an oxide semiconductor contains a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state. (See FIG. 1B).

For example, the oxygen concentration in the amorphous oxide semiconductor film 441 introduced by the oxygen 431 introduction step is preferably set to 1 × 10 18 / cm 3 or more and 3 × 10 21 / cm 3 or less. In addition, the oxygen excess region may be present in a part (including an interface) of the amorphous oxide semiconductor film 441. Therefore, by introducing oxygen 431, in the lamination of the gate insulating film 402, the amorphous oxide semiconductor film 441, and the insulating film 407, the interface between the gate insulating film 402 and the amorphous oxide semiconductor film 441, Oxygen is contained in the amorphous oxide semiconductor film 441 or at least one of the interfaces between the amorphous oxide semiconductor film 441 and the insulating film 407.

The amorphous oxide semiconductor film 441 includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. In this case, the content of oxygen is such that it exceeds the stoichiometric composition ratio of the oxide semiconductor. Alternatively, the content of oxygen is such that it exceeds the amount of oxygen in the case of a single crystal. Oxygen may exist between the lattice of an oxide semiconductor. The composition of such an oxide semiconductor can be expressed as InGaZn m O m + 3x (x> 1). For example, when m = 1, the composition of the oxide semiconductor is InGaZnO 1 + 3x (x> 1), and in the case of excess oxygen, 1 + 3x represents a value exceeding 4.

The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 441.

In addition, the amorphous state in the amorphous oxide semiconductor film 441 can be made more uniform by the introduction process of oxygen 431.

In the oxide semiconductor, oxygen is one of the main component materials. For this reason, it is difficult to accurately estimate the oxygen concentration in the oxide semiconductor film using a method such as Secondary Ion Mass Spectrometry (SIMS). That is, it can be said that it is difficult to determine whether oxygen was intentionally added to the oxide semiconductor film.

By the way, the oxygen, the isotope is present and the ratio of these in the natural world, such as 17 O and 18 O is known that the each of 0.037% of the oxygen atoms, 0.204% or so. That is, since the concentration of these isotopes in the oxide semiconductor film is estimated by the method such as SIMS, it is possible to estimate the oxygen concentration in the oxide semiconductor film more accurately by measuring these concentrations. There is. Therefore, by measuring these concentrations, it may be determined whether oxygen is intentionally added to the oxide semiconductor film.

As in the present embodiment, when oxygen 431 is directly introduced into the amorphous oxide semiconductor film 441, an insulating film (gate insulating film 402, insulating film 407, etc.) in contact with the amorphous oxide semiconductor film 441 is used. Although not necessarily a film containing a large amount of oxygen, an insulating film (gate insulating film 402, insulating film 407, etc.) in contact with the amorphous oxide semiconductor film 441 is a film containing a large amount of oxygen, and the oxygen ( 431 may be introduced directly into the amorphous oxide semiconductor film 441 to perform a plurality of oxygen supply methods.

Next, the amorphous oxide semiconductor film 441 is processed into an island-shaped amorphous oxide semiconductor film 443 by a second photolithography process (see FIG. 1C). Further, a resist mask for forming the island-shaped amorphous oxide semiconductor film 443 may be formed by the inkjet method. When the resist mask is formed by the inkjet method, the photomask is not used, and thus manufacturing cost can be reduced.

In addition, in one aspect of the disclosed invention, the oxide semiconductor film (amorphous oxide semiconductor film and crystalline oxide semiconductor film) may be processed into island shapes as shown in this embodiment, and the film shape is not processed without processing the shape. You may leave it as it is.

In the case where a contact hole is formed in the gate insulating film 402, the process can be performed simultaneously when the amorphous oxide semiconductor film 443 is processed.

The etching of the amorphous oxide semiconductor film 441 herein may be either dry etching or wet etching, or both may be used. For example, as an etching liquid used for wet etching of the amorphous oxide semiconductor film 441, a solution in which phosphoric acid, acetic acid and nitric acid are mixed, and the like can be used. Moreover, you may use ITO07N (made by Kanto Chemical).

Subsequently, a conductive film serving as a source electrode layer and a drain electrode layer (including a wiring formed in the same layer) is formed over the gate insulating film 402 and the amorphous oxide semiconductor film 443. The conductive film is made of a material that can withstand later heat treatment. As the conductive film used for the source electrode layer and the drain electrode layer, for example, a metal film containing an element selected from Al, Cr, Cu, Ta, Ti, Mo, W, or a metal nitride film containing the above element as a component. (Titanium nitride film, molybdenum nitride film, tungsten nitride film) and the like can be used. Further, a structure in which a high melting point metal film such as Ti, Mo, W, or these metal nitride films (titanium nitride film, molybdenum nitride film, tungsten nitride film) are laminated on one or both of the lower and upper sides of metal films such as Al and Cu, etc. You may make it. In addition, you may form with electroconductive metal oxide as a conductive film used for a source electrode layer and a drain electrode layer. Examples of conductive metal oxides include indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), zinc oxide (ZnO), indium tin oxide (In 2 O 3 -SnO 2 ), and indium zinc oxide (In 2 O 3). -ZnO) or those in which silicon oxide is contained in these metal oxide materials can be used.

A resist mask is formed on the conductive film by the third photolithography step, and selectively etched to form the source electrode layer 405a and the drain electrode layer 405b, and then the resist mask is removed.

In addition, in order to reduce the number of photomasks and process number used in a photolithography process, you may perform an etching process using the resist mask formed by the multi-gradation mask which is an exposure mask in which the transmitted light becomes several intensity | strength. Since the resist mask formed using a multi gradation mask becomes a shape which has a some film thickness, and can change shape again by performing an etching, it can be used for the some etching process processed into a different pattern. Therefore, the resist mask corresponding to at least two or more types of different patterns can be formed with one multi-tone mask. Therefore, since the number of exposure masks can be reduced and the corresponding photolithography process can also be reduced, the process can be simplified.

In addition, during etching of the conductive film, it is desirable to optimize the etching conditions so that the amorphous oxide semiconductor film 443 is etched and not segmented. However, it is difficult to obtain a condition that only the conductive film is etched and that the amorphous oxide semiconductor film 443 is not etched at all. Only a part of the amorphous oxide semiconductor film 443 is etched at the time of etching the conductive film, so that the grooves (concave portions) It may become an oxide semiconductor film which has.

In this embodiment, since the Ti film is used as the conductive film, and the In-Ga-Zn-based oxide semiconductor is used for the amorphous oxide semiconductor film 443, ammonia fruit water (a mixture of ammonia, water, and hydrogen peroxide solution) is used as the etching solution. do.

Next, an insulating film 407 in contact with a portion of the amorphous oxide semiconductor film 443 is formed (see FIG. 1D). Although the insulating film 407 may be a single layer or lamination, it is set as the structure containing an aluminum oxide film.

The film thickness of the aluminum oxide film contained in the insulating film 407 is 30 nm or more and 500 nm or less, Preferably it is 50 nm or more and 200 nm or less. The insulating film 407 can be formed by appropriately using a method such as sputtering that does not mix impurities such as water and hydrogen into the insulating film 407. When hydrogen is contained in the insulating film 407, the hydrogen penetrates into the oxide semiconductor film or the oxygen is extracted from the oxide semiconductor film by hydrogen, and the back channel of the oxide semiconductor film is reduced in resistance (N-type), resulting in parasitics. There is a fear that a channel is formed. Therefore, it is important not to use hydrogen in the film formation method so that the insulating film 407 becomes a film containing no hydrogen as much as possible.

It is preferable that the aluminum oxide film also includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the aluminum oxide crystal state. In this case, the content of oxygen is such that it exceeds the stoichiometric composition ratio of aluminum oxide. Alternatively, the content of oxygen is such that it exceeds the amount of oxygen in the case of a single crystal. Oxygen may exist between lattice of aluminum oxide. When the composition is expressed by AlO x (x> 0), it is preferable to use an aluminum oxide film in which x has an excess oxygen region of more than 3/2. Such oxygen excess region should just exist in a part (including an interface) of an aluminum oxide film.

In this embodiment, an aluminum oxide film having a thickness of 100 nm is formed as the insulating film 407 by using a sputtering method. Film formation by the sputtering method of an aluminum oxide film can be performed in a rare gas (typically argon) atmosphere, oxygen atmosphere, or mixed atmosphere of a rare gas and oxygen.

As in the case of forming an oxide semiconductor film, in order to remove residual moisture in the film formation chamber of the insulating film 407, it is preferable to use an adsorption type vacuum pump (such as a cryo pump). The concentration of impurities contained in the insulating film 407 formed in the film formation chamber exhausted using the cryopump can be reduced. As the exhaust means for removing residual moisture in the film formation chamber of the insulating film 407, cold trap may be applied to the turbomolecular pump.

As the sputtering gas used for forming the insulating film 407, it is preferable to use a high purity gas from which impurities such as hydrogen, water, hydroxyl groups, or hydrides are removed.

In the case where the insulating film 407 is laminated, an inorganic insulating film such as a silicon oxide film, a silicon oxynitride film, an aluminum oxynitride film, or a gallium oxide film can be typically used in addition to the aluminum oxide film. 10A shows an example of the transistor 410a in which the insulating film 407 has a stacked structure of the insulating film 407a and the insulating film 407b.

As shown in Fig. 10A, an insulating film 407a is formed over the crystalline oxide semiconductor film 403, the source electrode layer 405a, and the drain electrode layer 405b, and an insulating film 407b is formed over the insulating film 407a. The insulating film 407a is preferable because an oxide insulating film containing an excess oxygen content becomes a source of oxygen to the crystalline oxide semiconductor film 403. For example, in this embodiment, as the insulating film 407a, a silicon oxide film containing a region in which oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state is used, and the insulating film 407b is used. As the aluminum oxide film is used.

Next, the amorphous oxide semiconductor film 443 is subjected to heat treatment to crystallize at least a portion of the amorphous oxide semiconductor film 443 to form a crystalline oxide semiconductor film 403 including crystals. In this embodiment, the crystalline oxide semiconductor film 403 includes crystals having a c-axis that is approximately perpendicular to the surface.

The aluminum oxide film formed as the insulating film 407 on the amorphous oxide semiconductor film 443 has a high blocking effect (block effect) that does not allow the film to pass through both impurities such as hydrogen and water and oxygen.

Therefore, the aluminum oxide film is mixed in the oxide semiconductor film (amorphous oxide semiconductor film 443 and the crystalline oxide semiconductor film 403) of impurities such as hydrogen and moisture, which are factors of variation during and after the fabrication process, And a protective film which prevents emission of oxygen semiconductor films (amorphous oxide semiconductor film 443 and crystalline oxide semiconductor film 403) which are main component materials constituting the oxide semiconductor.

Since the heat treatment for crystallizing the amorphous oxide semiconductor film 443 is performed in a state where the amorphous oxide semiconductor film 443 is covered by the aluminum oxide film formed as the insulating film 407, the amorphous oxide semiconductor is subjected to heat treatment for crystallization. The release of oxygen from the film 443 can be prevented. Therefore, the obtained crystalline oxide semiconductor film 403 maintains the amount of oxygen contained in the amorphous oxide semiconductor film 443 and includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. I can do it.

In the crystalline oxide semiconductor film 403, oxygen vacancies exist at a place where oxygen is released. An oxide semiconductor which does not contain oxygen excessively cannot supplement the deficiency with other oxygen even if an oxygen deficiency occurs. However, the crystalline oxide semiconductor film 403 of one embodiment of the disclosed invention is a crystalline oxide semiconductor film containing an excess of oxygen (in this embodiment, a semiconductor containing a crystal having a c-axis approximately perpendicular to the surface). (CAAC-OS) film) and the crystalline oxide semiconductor film 403 contains excess oxygen (preferably excess oxygen than the stoichiometric composition ratio) in the film even if oxygen deficiency occurs. Oxygen acts on the missing part and can immediately replenish the missing part.

Therefore, by using the crystalline oxide semiconductor film 403 for the transistor 410, the deviation of the threshold voltage Vth and the shift ΔVth of the threshold voltage due to the oxygen deficiency can be reduced. Can be.

The temperature of the heat treatment for crystallizing at least a part of the amorphous oxide semiconductor film 443 is 250 ° C or more and 700 ° C or less, preferably 400 ° C or more, more preferably 500 ° C, even more preferably 550 ° C or more.

For example, a board | substrate is introduce | transduced into the electric furnace which is one of heat processing apparatuses, and heat processing for 1 hour is performed at 450 degreeC under oxygen atmosphere with respect to an oxide semiconductor film.

In addition, the heat processing apparatus is not limited to an electric furnace, You may use the apparatus which heats a to-be-processed object by heat conduction or heat radiation from a heat generating body, such as a resistance heating body. For example, a Rapid Thermal Anneal (RTA) device such as a Gas Rapid Thermal Anneal (GRTA) device or a Lamp Rapid Thermal Anneal (LRTA) device may be used. An LRTA apparatus is an apparatus which heats a to-be-processed object by the radiation of the light (electromagnetic wave) emitted from lamps, such as a halogen lamp, a metal halide lamp, a xenon arc lamp, a carbon arc lamp, a high pressure sodium lamp, and a high pressure mercury lamp. A GRTA apparatus is an apparatus which heat-processes using high temperature gas. As the hot gas, a rare gas such as argon or an inert gas such as nitrogen, which does not react with the object to be processed by heat treatment is used.

For example, as a heat treatment, a substrate may be put in an inert gas heated at a high temperature of 650 ° C to 700 ° C, heated for a few minutes, and then GRTA may be carried out in the inert gas.

As the heat treatment for crystallization, heat treatment by light irradiation with laser light, lamp light or the like may be used. For example, the amorphous oxide semiconductor film can be crystallized by irradiating a laser beam having a wavelength absorbed by the amorphous oxide semiconductor film.

The heat treatment may be performed in an atmosphere of nitrogen, oxygen, ultra-dried air (air with water content of 20 ppm or less, preferably 1 ppm or less, preferably 10 ppm or less) or rare gas (argon, helium, etc.). It is preferable that water, hydrogen, etc. are not contained in atmospheres, such as super dry air or a rare gas. Further, the purity of nitrogen, oxygen, or rare gas introduced into the heat treatment apparatus is 6N (99.9999%) or more, preferably 7N (99.99999%) or more (that is, impurity concentration is 1 ppm or less, preferably 0.1 ppm or less). It is desirable to.

In the crystalline oxide semiconductor film 403 which has become highly purified and supplemented with oxygen deficiency, impurities such as hydrogen and water are sufficiently removed, and the hydrogen concentration in the crystalline oxide semiconductor film 403 is 5 × 10 19 / cm 3 or less. Preferably, it is 5 * 10 <18> / cm <3> or less. In addition, the hydrogen concentration in the crystalline oxide semiconductor film 403 is measured by Secondary Ion Mass Spectrometry (SIMS).

In such a crystalline oxide semiconductor film 403, there are very few carriers (close to zero), and the carrier concentration is less than 1 × 10 14 / cm 3, preferably less than 1 × 10 12 / cm 3, more preferably 1 × 10 11. Less than / cm 3.

The transistor 410 is formed by the above process (see FIG. 1E). The transistor 410 is a transistor having a crystalline oxide semiconductor film that is highly purified and contains an excess of oxygen to compensate for oxygen deficiency. Therefore, the transistor 410 is suppressed from fluctuation in electrical characteristics and is electrically stable.

The transistor 410 using the crystalline oxide semiconductor film 403 which has been made highly purified using the present embodiment and contains an excess of oxygen to compensate for the oxygen deficiency, has a current value (off current value in an off state). ), At a room temperature per 1 μm of channel width, 100 zA / μm (1zA (p-ampere) is 1 × 10 −21 A) or less, preferably 10 zA / μm or less, more preferably 1 zA / μm or less, still more preferably It can be made low to the level of 100yA / micrometer or less.

As described above, a semiconductor device using an oxide semiconductor having stable electrical characteristics can be provided. Therefore, a highly reliable semiconductor device can be provided.

This embodiment can be implemented in appropriate combination with any of the other embodiments.

(Embodiment 2)

In this embodiment, another embodiment of the semiconductor device and the manufacturing method of the semiconductor device will be described with reference to FIG. 2. The part and the process which have the same part or the same function as the said embodiment can be performed similarly to the said embodiment, and repeated description is abbreviate | omitted. In addition, detailed description of the same location is abbreviate | omitted.

In this embodiment, in the method of manufacturing a semiconductor device according to the disclosed invention, an example in which an oxygen introduction step into an amorphous oxide semiconductor film is performed through an insulating film formed over the transistor 410 is shown.

2A to 2E show an example of the manufacturing method of the transistor 410 in the present embodiment.

After the conductive film is formed on the substrate 400 having the insulating surface, the gate electrode layer 401 is formed.

Next, the gate insulating film 402 is formed on the gate electrode layer 401 by plasma CVD, sputtering, or the like.

Subsequently, an amorphous oxide semiconductor film 491 having a thickness of 2 nm or more and 200 nm or less, preferably 5 nm or more and 30 nm or less is formed on the gate insulating film 402 (see FIG. 2A).

The amorphous oxide semiconductor film 491 may be subjected to a heat treatment for removing (dehydrating or dehydrogenating) excess hydrogen (including water and hydroxyl groups).

Next, the amorphous oxide semiconductor film 491 is processed into an island-shaped amorphous oxide semiconductor film 492 by a photolithography process (see FIG. 2B).

Next, a source electrode layer 405a and a drain electrode layer 405b are formed over the gate insulating film 402 and the amorphous oxide semiconductor film 492.

Next, an insulating film 407 in contact with a portion of the amorphous oxide semiconductor film 492 is formed (see FIG. 2C). Although the insulating film 407 may be a single layer or lamination, it is set as the structure containing an aluminum oxide film.

In this embodiment, an aluminum oxide film having a thickness of 100 nm is formed as the insulating film 407 by using a sputtering method.

Next, oxygen 431 (including at least one of oxygen radicals, oxygen atoms, and oxygen ions) is introduced into the amorphous oxide semiconductor film 492, and oxygen is supplied to the amorphous oxide semiconductor film 492. .

In the present embodiment, after the insulating film 407 is formed, oxygen 431 is injected into the amorphous oxide semiconductor film 492 by passing through the insulating film 407 by an ion implantation method. By the implantation process of oxygen 431, the amorphous oxide semiconductor film 492 has an amorphous oxide semiconductor film 443 in which an oxide semiconductor contains a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state. (See FIG. 2D).

The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 443.

In addition, depending on the oxygen introduction conditions, oxygen can be introduced into a portion of the insulating film (and the interface between the insulating film and the amorphous oxide semiconductor film) when the oxygen is introduced through the insulating film and into the amorphous oxide semiconductor film. For example, when the insulating film has a laminated structure of an oxide insulating film (for example, a silicon oxide film) and an aluminum oxide film, an oxide insulating film, an amorphous oxide semiconductor film, and an oxide insulating film contacting the amorphous oxide semiconductor film when oxygen is introduced into the amorphous oxide semiconductor film; Oxygen may also be introduced into the interface of the oxide insulating film to form an excess oxygen region in the lamination of the amorphous oxide semiconductor film and the oxide insulating film.

Next, the amorphous oxide semiconductor film 443 is subjected to heat treatment to crystallize at least a part of the amorphous oxide semiconductor film 443 to form a crystalline oxide semiconductor film 403.

In this embodiment, the crystalline oxide semiconductor film 403 is formed as the crystalline oxide semiconductor film 403 including a crystal having a c-axis approximately perpendicular to the surface.

The aluminum oxide film formed as the insulating film 407 on the amorphous oxide semiconductor film 443 has a high blocking effect (block effect) that does not allow the film to pass through both impurities such as hydrogen and water and oxygen.

Therefore, the aluminum oxide film is mixed in the oxide semiconductor film (amorphous oxide semiconductor film 443 and the crystalline oxide semiconductor film 403) of impurities such as hydrogen and moisture, which are factors of variation during and after the fabrication process, And a protective film which prevents emission of oxygen semiconductor films (amorphous oxide semiconductor film 443 and crystalline oxide semiconductor film 403) which are main component materials constituting the oxide semiconductor.

Since the heat treatment for crystallizing the amorphous oxide semiconductor film 443 is performed in a state where the amorphous oxide semiconductor film 443 is covered by the aluminum oxide film formed as the insulating film 407, the amorphous oxide semiconductor is subjected to heat treatment for crystallization. The release of oxygen from the film 443 can be prevented. Therefore, the obtained crystalline oxide semiconductor film 403 maintains the amount of oxygen contained in the amorphous oxide semiconductor film 443 and includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. I can do it.

Therefore, the crystalline oxide semiconductor film 403 formed is of high purity because the incorporation of impurities such as hydrogen and moisture and the release of excess oxygen are prevented by the aluminum oxide film, so that the oxide semiconductor is in a crystalline state. Regarding the stoichiometric composition ratio in the above, the oxygen content includes an excess region.

In the crystalline oxide semiconductor film 403, oxygen vacancies exist at a place where oxygen is released. An oxide semiconductor which does not contain oxygen excessively cannot supplement the deficiency with other oxygen even if an oxygen deficiency occurs. However, the crystalline oxide semiconductor film 403 of one embodiment of the disclosed invention is a film containing excessive oxygen (in this embodiment, a CAAC-OS film containing excess oxygen), and is a crystalline oxide semiconductor film. 403 indicates that even if an oxygen deficiency occurs, by containing excess oxygen (preferably excess oxygen than the stoichiometric composition ratio) in the film, the excess oxygen acts on the defective part and can immediately replenish the defective part with oxygen. have.

The transistor 410 is formed by the above process (see FIG. 2E). The transistor 410 is a transistor having a crystalline oxide semiconductor film that is highly purified and contains an excess of oxygen to compensate for oxygen deficiency. Therefore, the transistor 410 is suppressed from fluctuation in electrical characteristics and is electrically stable.

As described above, a semiconductor device using an oxide semiconductor having stable electrical characteristics can be provided. Therefore, a highly reliable semiconductor device can be provided.

This embodiment can be implemented in appropriate combination with any of the other embodiments.

(Embodiment 3)

In this embodiment, another embodiment of the semiconductor device and the manufacturing method of the semiconductor device will be described with reference to FIG. 3. The part and the process which have the same part or the same function as the said embodiment can be performed similarly to the said embodiment, and repeated description is abbreviate | omitted. In addition, detailed description of the same location is abbreviate | omitted.

The transistor 430 shown in FIGS. 3A to 3E is an example of a transistor having a bottom gate structure.

The transistor 430 includes a gate electrode layer 401, a gate insulating film 402, a source electrode layer 405a, a drain electrode layer 405b, and a crystalline oxide semiconductor film 403 on a substrate 400 having an insulating surface. Include. An insulating film 407 is formed to cover the transistor 430.

3A to 3E show an example of the manufacturing method of the transistor 430.

First, a gate electrode layer 401 is formed over a substrate 400 having an insulating surface (see FIG. 3A).

A gate insulating film 402 is formed on the gate electrode layer 401. In this embodiment, a silicon oxide film is used for the gate insulating film 402.

The silicon oxide film in contact with the crystalline oxide semiconductor film 403 preferably includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio of the silicon oxide in the crystal state.

By making the silicon oxide film in contact with the crystalline oxide semiconductor film 403 contain a large amount of oxygen, it can function suitably as a supply source for supplying oxygen to the oxide semiconductor film.

Next, a source electrode layer 405a and a drain electrode layer 405b are formed over the gate insulating film 402.

Subsequently, an amorphous oxide semiconductor film is formed on the gate insulating film 402, the source electrode layer 405a, and the drain electrode layer 405b, and processed into an island shape to form an amorphous oxide semiconductor film 492 (see FIG. 3B).

As the amorphous oxide semiconductor film 492, in this embodiment, an In—Ga—Zn oxide film is formed by sputtering using an In—Ga—Zn oxide oxide target.

The amorphous oxide semiconductor film 492 may also be subjected to a heat treatment for removing (dehydrating or dehydrogenating) excess hydrogen (including water and hydroxyl groups). The temperature of the heat treatment is a temperature at which the amorphous oxide semiconductor film 492 is not crystallized, and is typically 250 ° C. or more and 400 ° C. or less, preferably 300 ° C. or less.

The heat treatment for dehydration or dehydrogenation may be performed before the amorphous oxide semiconductor film 492 is processed into island shapes.

Next, oxygen 431 (including at least one of oxygen radicals, oxygen atoms, and oxygen ions) is introduced into the amorphous oxide semiconductor film 492, and oxygen is supplied to the amorphous oxide semiconductor film 492. .

In this embodiment, oxygen 431 is injected into the exposed amorphous oxide semiconductor film 492 by the ion implantation method. By the implantation process of oxygen 431, the amorphous oxide semiconductor film 492 has an amorphous oxide semiconductor film 443 in which an oxide semiconductor contains a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state. (See FIG. 3C).

The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 443.

Next, an insulating film 407 is formed over the amorphous oxide semiconductor film 443 (see FIG. 3D). Although the insulating film 407 may be a single layer or lamination, it is set as the structure containing an aluminum oxide film.

The film thickness of the aluminum oxide film contained in the insulating film 407 is 30 nm or more and 500 nm or less, Preferably it is 50 nm or more and 200 nm or less.

It is preferable that the aluminum oxide film also includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the aluminum oxide crystal state.

In this embodiment, an aluminum oxide film having a thickness of 100 nm is formed as the insulating film 407 by using a sputtering method.

Next, the amorphous oxide semiconductor film 443 is subjected to heat treatment to crystallize at least a part of the amorphous oxide semiconductor film 443 to form a crystalline oxide semiconductor film 403.

The temperature of the heat treatment for crystallizing at least a part of the amorphous oxide semiconductor film 443 is 250 ° C or more and 700 ° C or less, preferably 400 ° C or more, more preferably 500 ° C, even more preferably 550 ° C or more.

In this embodiment, the crystalline oxide semiconductor film 403 is formed as the crystalline oxide semiconductor film 403 including a crystal having a c-axis approximately perpendicular to the surface.

The aluminum oxide film formed as the insulating film 407 on the amorphous oxide semiconductor film 443 has a high blocking effect (block effect) that does not allow the film to pass through both impurities such as hydrogen and water and oxygen.

Therefore, the aluminum oxide film is mixed in the oxide semiconductor film (amorphous oxide semiconductor film 443 and the crystalline oxide semiconductor film 403) of impurities such as hydrogen and moisture, which are factors of variation during and after the fabrication process, And a protective film which prevents emission of oxygen semiconductor films (amorphous oxide semiconductor film 443 and crystalline oxide semiconductor film 403) which are main component materials constituting the oxide semiconductor.

Since the heat treatment for crystallizing the amorphous oxide semiconductor film 443 is performed in a state where the amorphous oxide semiconductor film 443 is covered by the aluminum oxide film formed as the insulating film 407, the amorphous oxide semiconductor is subjected to heat treatment for crystallization. The release of oxygen from the film 443 can be prevented. Therefore, the obtained crystalline oxide semiconductor film 403 maintains the amount of oxygen contained in the amorphous oxide semiconductor film 443 and includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. I can do it.

Therefore, the crystalline oxide semiconductor film 403 formed is of high purity because the incorporation of impurities such as hydrogen and moisture and the release of excess oxygen are prevented by the aluminum oxide film, so that the oxide semiconductor is in a crystalline state. Regarding the stoichiometric composition ratio in the above, the oxygen content includes an excess region.

In the crystalline oxide semiconductor film 403, oxygen vacancies exist at a place where oxygen is released. An oxide semiconductor which does not contain oxygen excessively cannot supplement the deficiency with other oxygen even if an oxygen deficiency occurs. However, the crystalline oxide semiconductor film 403 of one embodiment of the disclosed invention is a film containing excessive oxygen (in this embodiment, a CAAC-OS film containing excess oxygen), and is a crystalline oxide semiconductor film. 403 indicates that even if an oxygen deficiency occurs, it contains excess oxygen (preferably excess oxygen than the stoichiometric composition ratio) in the film, so that the excess oxygen acts on the defective part and immediately replenishes the defective part. Can be.

Therefore, by using the crystalline oxide semiconductor film 403 for the transistor 430, the deviation of the threshold voltage Vth and the shift ΔVth of the threshold voltage due to the oxygen deficiency can be reduced. Can be.

The transistor 430 is formed by the above process (see FIG. 3E). The transistor 430 is a transistor having a crystalline oxide semiconductor film that is highly purified and contains an excess of oxygen to compensate for oxygen deficiency. Therefore, the transistor 430 is suppressed from fluctuation in electrical characteristics and is electrically stable.

The transistor 430 using the crystalline oxide semiconductor film 403 which has been made highly purified using the present embodiment and contains excessive oxygen to compensate for the oxygen deficiency has a current value (off current value in an off state). ), At a room temperature per 1 μm of channel width, 100 zA / μm (1zA (p-ampere) is 1 × 10 −21 A) or less, preferably 10 zA / μm or less, more preferably 1 zA / μm or less, still more preferably It can be made low to the level of 100yA / micrometer or less.

As described above, a semiconductor device using an oxide semiconductor having stable electrical characteristics can be provided. Therefore, a highly reliable semiconductor device can be provided.

This embodiment can be implemented in appropriate combination with any of the other embodiments.

(Embodiment 4)

In this embodiment, another embodiment of the semiconductor device and the manufacturing method of the semiconductor device will be described with reference to FIG. 4. The part and the process which have the same part or the same function as the said embodiment can be performed similarly to the said embodiment, and repeated description is abbreviate | omitted. In addition, detailed description of the same location is abbreviate | omitted.

In this embodiment, in the method of manufacturing a semiconductor device according to the disclosed invention, an example is described in which an oxygen introduction step into an amorphous oxide semiconductor film is performed through an insulating film formed over the transistor 430.

The transistor 430 illustrated in FIGS. 4A to 4E is an example of a transistor having a bottom gate structure. 4A to 4E show an example of the manufacturing method of the transistor 430.

First, a gate electrode layer 401 is formed over a substrate 400 having an insulating surface (see FIG. 4A).

A gate insulating film 402 is formed on the gate electrode layer 401. In this embodiment, a silicon oxide film is used for the gate insulating film 402.

The silicon oxide film in contact with the crystalline oxide semiconductor film 403 preferably includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio of the silicon oxide in the crystal state.

By making the silicon oxide film in contact with the crystalline oxide semiconductor film 403 contain a large amount of oxygen, it can function suitably as a supply source for supplying oxygen to the oxide semiconductor film.

Next, a source electrode layer 405a and a drain electrode layer 405b are formed over the gate insulating film 402.

Subsequently, an amorphous oxide semiconductor film is formed on the gate insulating film 402, the source electrode layer 405a, and the drain electrode layer 405b, and processed into islands to form an amorphous oxide semiconductor film 492 (see FIG. 4B).

As the amorphous oxide semiconductor film 492, in this embodiment, an In—Ga—Zn oxide film is formed by sputtering using an In—Ga—Zn oxide oxide target.

The amorphous oxide semiconductor film 492 may also be subjected to a heat treatment for removing (dehydrating or dehydrogenating) excess hydrogen (including water and hydroxyl groups). The temperature of the heat treatment is a temperature at which the amorphous oxide semiconductor film 492 is not crystallized, and is typically 250 ° C. or more and 400 ° C. or less, preferably 300 ° C. or less.

The heat treatment for dehydration or dehydrogenation may be performed before the amorphous oxide semiconductor film 492 is processed into island shapes.

Next, an insulating film 407 is formed over the amorphous oxide semiconductor film 492 (see FIG. 4C). Although the insulating film 407 may be a single layer or lamination, it is set as the structure containing an aluminum oxide film.

The film thickness of the aluminum oxide film contained in the insulating film 407 is 30 nm or more and 500 nm or less, Preferably it is 50 nm or more and 200 nm or less.

It is preferable that the aluminum oxide film also includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the aluminum oxide crystal state.

In this embodiment, an aluminum oxide film having a thickness of 100 nm is formed as the insulating film 407 by using a sputtering method.

Next, oxygen 431 (including at least one of oxygen radicals, oxygen atoms, and oxygen ions) is introduced into the amorphous oxide semiconductor film 492, and oxygen is supplied to the amorphous oxide semiconductor film 492. .

In the present embodiment, after the insulating film 407 is formed, oxygen 431 is injected into the amorphous oxide semiconductor film 492 through the insulating film 407 by an ion implantation method. By the implantation process of oxygen 431, the amorphous oxide semiconductor film 492 has an amorphous oxide semiconductor film 443 in which an oxide semiconductor contains a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state. (See FIG. 4D).

The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 443.

Next, the amorphous oxide semiconductor film 443 is subjected to heat treatment to crystallize at least a part of the amorphous oxide semiconductor film 443 to form a crystalline oxide semiconductor film 403.

The temperature of the heat treatment for crystallizing at least a part of the amorphous oxide semiconductor film 443 is 250 ° C or more and 700 ° C or less, preferably 400 ° C or more, more preferably 500 ° C, even more preferably 550 ° C or more.

In this embodiment, the crystalline oxide semiconductor film 403 is formed as the crystalline oxide semiconductor film 403 including a crystal having a c-axis approximately perpendicular to the surface.

The aluminum oxide film formed as the insulating film 407 on the amorphous oxide semiconductor film 443 has a high blocking effect (block effect) that does not allow the film to pass through both impurities such as hydrogen and water and oxygen.

Therefore, the aluminum oxide film is mixed in the oxide semiconductor film (amorphous oxide semiconductor film 443 and the crystalline oxide semiconductor film 403) of impurities such as hydrogen and moisture, which are factors of variation during and after the fabrication process, And a protective film which prevents emission of oxygen semiconductor films (amorphous oxide semiconductor film 443 and crystalline oxide semiconductor film 403) which are main component materials constituting the oxide semiconductor.

Since the heat treatment for crystallizing the amorphous oxide semiconductor film 443 is performed in a state where the amorphous oxide semiconductor film 443 is covered by the aluminum oxide film formed as the insulating film 407, the amorphous oxide semiconductor is subjected to heat treatment for crystallization. The release of oxygen from the film 443 can be prevented. Therefore, the obtained crystalline oxide semiconductor film 403 maintains the amount of oxygen contained in the amorphous oxide semiconductor film 443 and includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. I can do it.

Therefore, the crystalline oxide semiconductor film 403 formed is of high purity because the incorporation of impurities such as hydrogen and moisture and the release of excess oxygen are prevented by the aluminum oxide film, so that the oxide semiconductor is in a crystalline state. Regarding the stoichiometric composition ratio in the above, the oxygen content includes an excess region.

In the crystalline oxide semiconductor film 403, oxygen vacancies exist at a place where oxygen is released. An oxide semiconductor which does not contain oxygen excessively cannot supplement the deficiency with other oxygen even if an oxygen deficiency occurs. However, the crystalline oxide semiconductor film 403 of one embodiment of the disclosed invention is a film containing excessive oxygen (in this embodiment, a CAAC-OS film containing excess oxygen), and is a crystalline oxide semiconductor film. 403 indicates that even if an oxygen deficiency occurs, by containing excess oxygen (preferably excess oxygen than the stoichiometric composition ratio) in the film, the excess oxygen acts on the defective part and can immediately replenish the defective part with oxygen. have.

The transistor 430 is formed by the above process (see FIG. 4E). The transistor 430 is a transistor having a crystalline oxide semiconductor film that is highly purified and contains an excess of oxygen to compensate for oxygen deficiency. Therefore, the transistor 430 is suppressed from fluctuation in electrical characteristics and is electrically stable.

As described above, a semiconductor device using an oxide semiconductor having stable electrical characteristics can be provided. Therefore, a highly reliable semiconductor device can be provided.

This embodiment can be implemented in appropriate combination with any of the other embodiments.

(Embodiment 5)

In this embodiment, one embodiment of the semiconductor device and the manufacturing method of the semiconductor device will be described with reference to FIG. 5. In this embodiment, a transistor having an oxide semiconductor film is shown as an example of a semiconductor device. The part and the process which have the same part or the same function as the said embodiment can be performed similarly to the said embodiment, and repeated description is abbreviate | omitted. In addition, detailed description of the same location is abbreviate | omitted.

The transistor 440 illustrated in FIGS. 5A to 5F is an example of a transistor having a top gate structure.

As shown in FIG. 5F, the transistor 440 is a source electrode layer 405a, a drain electrode layer 405b, and a crystalline oxide semiconductor film 403 on a substrate 400 having an insulating surface on which an insulating film 436 is formed. And a gate insulating film 402 and a gate electrode layer 401. An insulating film 407 is formed over the transistor 440.

Although the insulating film 407 may be a single layer or lamination, it is set as the structure containing an aluminum oxide film. In this embodiment, the insulating film 407 uses an aluminum oxide film.

In addition, the crystalline oxide semiconductor film 403 is an oxide semiconductor film having crystallinity, and in the present embodiment, includes a crystal having an ab plane parallel to the surface and having a c-axis that is approximately perpendicular to the surface. The oxide semiconductor film is not a single crystal structure, nor an amorphous structure, and is a crystalline oxide semiconductor (CAAC-OS) having a c-axis orientation. By using the crystalline oxide semiconductor film, a change in the electrical characteristics of the transistor due to the irradiation of visible light or ultraviolet light can be further suppressed and a highly reliable semiconductor device can be obtained.

5A to 5F show an example of a method of manufacturing the transistor 440.

First, an insulating film 436 is formed over a substrate 400 having an insulating surface.

As the insulating film 436, silicon oxide, silicon oxynitride, aluminum oxide, aluminum oxynitride, hafnium oxide, gallium oxide, silicon nitride, silicon nitride oxide, aluminum nitride, aluminum nitride oxide, or the like may be used by plasma CVD or sputtering. It can form using these mixed materials.

Although the insulating film 436 may be a single layer or lamination, it is preferable to use an oxide insulating film for the film which contacts the crystalline oxide semiconductor film 403. In this embodiment, a silicon oxide film formed using a sputtering method is used as the insulating film 436.

Next, an amorphous oxide semiconductor film 491 is formed over the insulating film 436 (see FIG. 5A).

Since the insulating film 436 is in contact with the amorphous oxide semiconductor film 491, it is preferable that oxygen in an amount exceeding at least the stoichiometric composition ratio is present in the film (in the bulk). For example, when a silicon oxide film is used as the insulating film 436, SiO 2 + α (where α> 0) is used. By using such an insulating film 436, oxygen can be supplied to the amorphous oxide semiconductor film 491, and the characteristics can be improved. By supplying oxygen to the amorphous oxide semiconductor film 491, oxygen deficiency in the film can be compensated for.

For example, an insulating film 436 containing a large amount (excess) of oxygen serving as an oxygen source is formed in contact with the amorphous oxide semiconductor film 491, thereby forming oxygen from the insulating film 436 to the amorphous oxide semiconductor film 491. Can be supplied. Oxygen may be supplied to the crystalline oxide semiconductor film 403 by performing a heating step in a state where at least part of the amorphous oxide semiconductor film 491 and the insulating film 436 are in contact with each other.

In the insulating film 436, the region where the crystalline oxide semiconductor film 403 (the amorphous oxide semiconductor film 491 is formed in contact with the process of FIG. 5A) is preferably a surface whose surface roughness is reduced. Specifically, the average surface roughness of the surface is preferably 1 nm or less, preferably 0.3 nm or less, and more preferably 0.1 nm or less. By forming the crystalline oxide semiconductor film 403 (the amorphous oxide semiconductor film 491 in the process of FIG. 5A) on the surface of which the surface roughness is reduced, the crystalline oxide semiconductor film 403 having stable and good crystallinity is obtained. Can be.

Therefore, the planarization process may be performed in the region where the crystalline oxide semiconductor film 403 (the amorphous oxide semiconductor film 491 in the process of FIG. 5A) is formed in the insulating film 436. Although it does not specifically limit as a planarization process, Polishing process (for example, a chemical mechanical polishing (CMP) method), a dry etching process, and a plasma process can be used.

As the plasma treatment, for example, reverse sputtering may be performed in which argon gas is introduced to generate plasma. Reverse sputtering is a method of modifying a surface by applying a voltage to the substrate side using an RF power supply in an argon atmosphere to form a plasma near the substrate. In addition, nitrogen, helium, oxygen, or the like may be used instead of the argon atmosphere. By reverse sputtering, the powdery substance (also called particles and dust) adhering to the surface of the insulating film 436 can be removed.

As the planarization treatment, the polishing treatment, the dry etching treatment and the plasma treatment may be performed a plurality of times, or a combination thereof may be performed. In addition, when performing in combination, process order is not specifically limited, either, According to the uneven | corrugated state of the surface of the insulating film 436, it is good to set suitably.

In the formation process of the amorphous oxide semiconductor film 491, in order to prevent hydrogen or water from containing in the amorphous oxide semiconductor film 491 as much as possible, as a pretreatment of the film formation of the amorphous oxide semiconductor film 491, It is preferable to preheat the substrate on which the insulating film 436 is formed in the preheating chamber, and to remove and exhaust impurities such as hydrogen and moisture adsorbed on the substrate and the insulating film 436. In addition, a cryopump is preferable for the exhaust means formed in the preheating chamber.

The film thickness of the amorphous oxide semiconductor film 491 is 1 nm or more and 200 nm or less (preferably 5 nm or more and 30 nm or less). The sputtering method, MBE (Molecular Beam Epitaxy) method, CVD method, pulse laser deposition method, ALD (Atomic) Layer Deposition) etc. can be used suitably.

In addition, the amorphous oxide semiconductor film 491 may be subjected to a heat treatment for removing (dehydrating or dehydrogenating) excess hydrogen (including water and hydroxyl groups). The temperature of the heat treatment is a temperature at which the amorphous oxide semiconductor film is not crystallized, and is typically 250 ° C. or more and 400 ° C. or less, preferably 300 ° C. or less.

The heat treatment can be performed under reduced pressure or under a nitrogen atmosphere. For example, a substrate is introduced into an electric furnace, which is one of the heat treatment apparatuses, and the heating process is performed for one hour at 450 ° C. under a nitrogen atmosphere to the oxide semiconductor film. After heating the amorphous oxide semiconductor film 491 by the heat treatment, high purity oxygen gas, high purity oxygen dioxygen gas, or ultra-dry air may be introduced into the same furnace. By the action of oxygen gas or oxygen dioxygen gas, it is possible to supply oxygen, which is a main component material constituting the amorphous oxide semiconductor, which has been simultaneously reduced by the step of removing impurities by dehydration or dehydrogenation treatment.

When the heating step for dehydration or dehydrogenation is performed before the amorphous oxide semiconductor film 491 is processed into an island shape into the amorphous oxide semiconductor film 492, oxygen contained in the insulating film 436 is released by the heating step. It is preferable because it can prevent that.

In addition, the amorphous oxide semiconductor film 491 may be processed in an island shape, or may be formed in a film shape without processing the shape. In addition, an element isolation region may be formed of an insulating film that separates the amorphous oxide semiconductor film 491 for each element.

In this embodiment, the amorphous oxide semiconductor film 491 is processed into an island-shaped amorphous oxide semiconductor film 492 by a photolithography process.

The etching of the amorphous oxide semiconductor film 491 may be dry etching or wet etching, or both may be used. For example, a solution obtained by mixing phosphoric acid, acetic acid, and nitric acid can be used as the etchant used for wet etching the amorphous oxide semiconductor film 491. Moreover, you may use ITO07N (made by Kanto Chemical).

Subsequently, a gate insulating film 442 covering the amorphous oxide semiconductor film 492 is formed (see FIG. 5B).

In addition, in order to improve the covering property of the gate insulating film 442 formed on the amorphous oxide semiconductor film 492, the planarization treatment may be performed on the surface of the amorphous oxide semiconductor film 492. In particular, when an insulating film having a thin film thickness is used as the gate insulating film 442, it is preferable that the flatness of the surface of the amorphous oxide semiconductor film 492 is good.

The film thickness of the gate insulating film 442 is 1 nm or more and 100 nm or less, and sputtering method, MBE method, CVD method, pulse laser deposition method, ALD method, etc. can be used suitably. The gate insulating film 442 may be formed by using a sputtering apparatus, a so-called CP sputtering apparatus, which forms a film in a state where a plurality of substrate surfaces are set substantially perpendicular to the sputtering target surface.

As the material of the gate insulating film 442, a silicon oxide film, a gallium oxide film, an aluminum oxide film, a silicon nitride film, a silicon oxynitride film, an aluminum oxynitride film, or a silicon nitride oxide film can be formed. The gate insulating film 442 preferably contains oxygen at a portion in contact with the amorphous oxide semiconductor film 492. In particular, the gate insulating film 442 preferably contains oxygen in an amount exceeding at least the stoichiometric composition ratio in the film (in the bulk). For example, when the silicon oxide film is used as the gate insulating film 442. Is set to SiO 2 + α (where α> 0). In this embodiment, as the gate insulating film 442, a silicon oxide film having SiO 2 + α (where α> 0) is used. By using this silicon oxide film as the gate insulating film 442, oxygen can be supplied to the amorphous oxide semiconductor film 492, and the characteristics can be improved. The gate insulating film 442 is preferably formed in consideration of the size of the transistor to be manufactured and the step coverage of the gate insulating film 442.

In addition, hafnium oxide, yttrium oxide, and hafnium silicate (HfSi x O y (x> 0, y> 0)) and hafnium silicate (HfSiO x N y (x> 0, The gate leakage current can be reduced by using high-k materials such as y> 0)), hafnium aluminate (HfAl x O y (x> 0, y> 0)), and lanthanum oxide. The gate insulating film 442 may have a single layer structure or a laminated structure.

Next, oxygen 431 (including at least one of oxygen radicals, oxygen atoms, and oxygen ions) is introduced into the amorphous oxide semiconductor film 492, and oxygen is supplied to the amorphous oxide semiconductor film 492. . As the method for introducing oxygen, an ion implantation method, an ion doping method, a plasma immersion ion implantation method, a plasma treatment, or the like can be used.

In the manufacturing process of the transistor 440 in the present embodiment, the oxygen introduction step is performed after the formation of the amorphous oxide semiconductor film 491 and before the aluminum oxide film is formed as the insulating film 407. In addition, the heat processing for dehydration or dehydrogenation is performed before oxygen introduction process. The oxygen introduction step may be introduced directly into the amorphous oxide semiconductor film, or may be introduced into the amorphous oxide semiconductor film through another film such as a gate insulating film or an insulating film. In the case where oxygen is introduced into the amorphous oxide semiconductor film through another film, an ion implantation method, an ion doping method, a plasma immersion ion implantation method, or the like may be used, but an amorphous oxide semiconductor film (for example, an amorphous oxide semiconductor film) to which oxygen is exposed After the formation of (491) and directly into the amorphous oxide semiconductor film 492), plasma treatment or the like can also be used.

In this embodiment, oxygen 431 is injected into the amorphous oxide semiconductor film 492 through the gate insulating film 442 by the ion implantation method. The implantation process of oxygen 431 results in an amorphous oxide semiconductor film 443 in which an oxide semiconductor contains a region having an excessive oxygen content with respect to the stoichiometric composition ratio in the crystal state (see FIG. 5C).

In addition, the amorphous state in the amorphous oxide semiconductor film 443 can be made more uniform by the introduction process of oxygen 431.

For example, the oxygen concentration in the amorphous oxide semiconductor film 443 introduced by the oxygen 431 introduction step is preferably set to 1 × 10 18 / cm 3 or more and 3 × 10 21 / cm 3 or less. In addition, the oxygen excess region may be present in a part (including an interface) of the amorphous oxide semiconductor film 443. Therefore, by introducing oxygen 431, the interface between the insulating film 436 and the amorphous oxide semiconductor film 443, the amorphous oxide semiconductor film 443, or the interface between the amorphous oxide semiconductor film 443 and the gate insulating film 442. Oxygen is contained in at least one of.

The amorphous oxide semiconductor film 443 includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. In this case, the content of oxygen is such that it exceeds the stoichiometric composition ratio of the oxide semiconductor. Alternatively, the content of oxygen is such that it exceeds the amount of oxygen in the case of a single crystal. Oxygen may exist between the lattice of an oxide semiconductor. The composition of such an oxide semiconductor can be expressed as InGaZn m O m + 3x (x> 1). For example, when m = 1, the composition of the oxide semiconductor is InGaZnO 1 + 3x (x> 1), and in the case of excess oxygen, 1 + 3x represents a value exceeding 4.

The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 443.

As in the present embodiment, when oxygen is directly introduced into the amorphous oxide semiconductor film, the insulating film in contact with the amorphous oxide semiconductor film is not necessarily a film containing much oxygen, but the insulating film in contact with the amorphous oxide semiconductor film, It may be a film containing a lot of oxygen, and oxygen may be directly introduced to the amorphous oxide semiconductor film to perform a plurality of oxygen supply methods.

The gate electrode layer 401 is formed on the gate insulating film 442. The material of the gate electrode layer 401 can be formed using a metal material such as molybdenum, titanium, tantalum, tungsten, aluminum, copper, chromium, neodymium, scandium, or an alloy material containing these as a main component. As the gate electrode layer 401, a silicide film such as a semiconductor film or a nickel silicide may be used, which is represented by a polycrystalline silicon film doped with an impurity element such as phosphorus. The gate electrode layer 401 may have a single layer structure or a laminated structure.

The material of the gate electrode layer 401 is indium tin oxide, indium oxide containing tungsten oxide, indium zinc oxide containing tungsten oxide, indium oxide containing titanium oxide, indium tin oxide containing titanium oxide, and indium. Electroconductive materials, such as indium tin oxide which added zinc oxide and silicon oxide, can also be applied. Moreover, it can also be set as the laminated structure of the said electroconductive material and the said metal material.

As one layer of the gate electrode layer 401 in contact with the gate insulating film 442, a metal oxide containing nitrogen, specifically, an In—Ga—Zn—O film containing nitrogen or an In— containing nitrogen. Sn-O film, In-Ga-O film containing nitrogen, In-Zn-O film containing nitrogen, Sn-O film containing nitrogen, In-O film containing nitrogen, Metal nitride films (InN, SnN, etc.) can be used. These films have a work function of 5 electron volts, preferably 5.5 electron volts or more, and when used as a gate electrode layer, the threshold voltage of the electrical characteristics of the transistor can be positive, and a so-called normally off switching element can be realized. .

Sidewall insulating layers 412a and 412b and sidewall insulating layers 402 having sidewall structures are formed on the side surfaces of the gate electrode layer 401. The sidewall insulating layers 412a and 412b form an insulating film covering the gate electrode layer 401, and then process the insulating film by anisotropic etching by a reactive ion etching (RIE) method, thereby forming a gate electrode layer ( The sidewall insulating layers 412a and 412b of the sidewall structure may be formed on the sidewall of the 401 in a self-aligning manner. Here, the insulating film is not particularly limited, but for example, silicon oxide having good step coverage formed by reacting TEOS (Tetraethyl-Ortho-Silicate) or silane with oxygen or nitrous oxide can be used. The insulating film can be formed by a method such as thermal CVD, plasma CVD, atmospheric pressure CVD, bias ECRCVD, sputtering, or the like. Moreover, you may use the silicon oxide formed by the Low Temperature Oxidation (LTO) method.

The gate insulating layer 402 may be formed by etching the gate insulating layer 442 using the gate electrode layer 401 and the sidewall insulating layers 412a and 412b as a mask.

In the present embodiment, when the insulating film is etched, the insulating film on the gate electrode layer 401 is removed and the gate electrode layer 401 is exposed, but the sidewall insulating layer 412a is formed to leave the insulating film on the gate electrode layer 401. , 412b). In addition, a protective film may be formed on the gate electrode layer 401 in a later step. By protecting the gate electrode layer 401 in this manner, it is possible to prevent film reduction of the gate electrode layer during etching. The etching method may be a dry etching method or a wet etching method, and various etching methods can be used.

Subsequently, a conductive film serving as a source electrode layer and a drain electrode layer (including wiring formed in the same layer) is formed on a portion of the sidewall insulating layers 412a and 412b and the amorphous oxide semiconductor film 443. The conductive film is made of a material that can withstand later heat treatment. As the conductive film used for the source electrode layer and the drain electrode layer, for example, a metal film containing an element selected from Al, Cr, Cu, Ta, Ti, Mo, W, or a metal nitride film containing the above element as a component. (Titanium nitride film, molybdenum nitride film, tungsten nitride film) and the like can be used. Further, a high melting point metal film such as Ti, Mo, W, or a metal nitride film thereof (titanium nitride film, molybdenum nitride film, tungsten nitride film) is laminated on one or both of the lower and upper sides of the metal film such as Al and Cu. It is good also as a structure. In addition, you may form with electroconductive metal oxide as a conductive film used for a source electrode layer and a drain electrode layer. Examples of conductive metal oxides include indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), zinc oxide (ZnO), indium tin oxide (In 2 O 3 -SnO 2 ), and indium zinc oxide (In 2 O 3). -ZnO) or those in which silicon oxide is contained in these metal oxide materials can be used.

A resist mask is formed on the conductive film by a photolithography step, and selectively etched to form the source electrode layer 405a and the drain electrode layer 405b, and then the resist mask is removed (see FIG. 5D).

Next, an insulating film 407 is formed over the gate electrode layer 401, the sidewall insulating layers 412a and 412b, the source electrode layer 405a, and the drain electrode layer 405b (see FIG. 5E). Although the insulating film 407 may be a single layer or lamination, it is set as the structure containing an aluminum oxide film.

The film thickness of the aluminum oxide film contained in the insulating film 407 is 30 nm or more and 500 nm or less, Preferably it is 50 nm or more and 200 nm or less. The insulating film 407 can be formed by appropriately using a method such as sputtering that does not mix impurities such as water and hydrogen into the insulating film 407. When hydrogen is contained in the insulating film 407, the hydrogen penetrates into the oxide semiconductor film or the oxygen is extracted from the oxide semiconductor film by hydrogen, resulting in a low resistance (N-type) of the oxide semiconductor film, thereby forming a parasitic channel. There is a concern. Therefore, it is important not to use hydrogen in the film formation method so that the insulating film 407 becomes a film containing no hydrogen as much as possible.

It is preferable that the aluminum oxide film also includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the aluminum oxide crystal state. In this case, the content of oxygen is such that it exceeds the stoichiometric composition ratio of aluminum oxide. Alternatively, the content of oxygen is such that it exceeds the amount of oxygen in the case of a single crystal. Oxygen may exist between lattice of aluminum oxide. When the composition is expressed by AlO x (x> 0), it is preferable to use an aluminum oxide film in which x has an excess oxygen region of more than 3/2. Such oxygen excess region should just exist in a part (including an interface) of an aluminum oxide film.

In this embodiment, an aluminum oxide film having a thickness of 100 nm is formed as the insulating film 407 by using a sputtering method. Film formation by the sputtering method of an aluminum oxide film can be performed in a rare gas (typically argon) atmosphere, oxygen atmosphere, or mixed atmosphere of a rare gas and oxygen.

As in the case of forming an oxide semiconductor film, in order to remove residual moisture in the film formation chamber of the insulating film 407, it is preferable to use an adsorption type vacuum pump (such as a cryo pump). The concentration of impurities contained in the insulating film 407 formed in the film formation chamber exhausted using the cryopump can be reduced. As the exhaust means for removing residual moisture in the film formation chamber of the insulating film 407, cold trap may be applied to the turbomolecular pump.

As the sputtering gas used for forming the insulating film 407, it is preferable to use a high purity gas from which impurities such as hydrogen, water, hydroxyl groups, or hydrides are removed.

In the case where the insulating film 407 is laminated, an inorganic insulating film such as a silicon oxide film, a silicon oxynitride film, an aluminum oxynitride film, or a gallium oxide film can be typically used in addition to the aluminum oxide film. In the transistor 440 in FIG. 10B, the transistor 440a is illustrated as an example in which the insulating film 407 has a stacked structure of the insulating film 407a and the insulating film 407b.

As shown in FIG. 10B, an insulating film 407a is formed on the gate electrode layer 401, the sidewall insulating layers 412a and 412b, the source electrode layer 405a, and the drain electrode layer 405b, and the insulating film 407a is formed on the insulating film 407a. 407b). For example, in this embodiment, as the insulating film 407a, a silicon oxide film containing an excessively oxygen-containing region with respect to the stoichiometric composition ratio in the crystal state is used as the silicon oxide insulating film 407b. As the aluminum oxide film is used.

Next, the amorphous oxide semiconductor film 443 is subjected to heat treatment to crystallize at least a portion of the amorphous oxide semiconductor film 443 to form a crystalline oxide semiconductor film 403 including crystals having a c-axis approximately perpendicular to the surface thereof. Form.

The aluminum oxide film formed as the insulating film 407 on the amorphous oxide semiconductor film 443 has a high blocking effect (block effect) that does not allow the film to pass through both impurities such as hydrogen and water and oxygen.

Therefore, the aluminum oxide film is mixed in the oxide semiconductor film (amorphous oxide semiconductor film 443 and the crystalline oxide semiconductor film 403) of impurities such as hydrogen and moisture, which are factors of variation during and after the fabrication process, And a protective film which prevents emission of oxygen semiconductor films (amorphous oxide semiconductor film 443 and crystalline oxide semiconductor film 403) which are main component materials constituting the oxide semiconductor.

Since the heat treatment for crystallizing the amorphous oxide semiconductor film 443 is performed in a state where the amorphous oxide semiconductor film 443 is covered by the aluminum oxide film formed as the insulating film 407, the amorphous oxide semiconductor is subjected to heat treatment for crystallization. The release of oxygen from the film 443 can be prevented. Therefore, the obtained crystalline oxide semiconductor film 403 maintains the amount of oxygen contained in the amorphous oxide semiconductor film 443 and includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. I can do it.

Therefore, the crystalline oxide semiconductor film 403 formed is of high purity because the incorporation of impurities such as hydrogen and moisture and the release of excess oxygen are prevented by the aluminum oxide film, and the oxide semiconductor is in a crystalline state. The stoichiometric composition ratio of includes a region in which the oxygen content is excessive.

In the crystalline oxide semiconductor film 403, oxygen vacancies exist at a place where oxygen is released. An oxide semiconductor which does not contain oxygen excessively cannot supplement the deficiency with other oxygen even if an oxygen deficiency occurs. However, the crystalline oxide semiconductor film 403 of one embodiment of the disclosed invention is a film containing excessive oxygen (in this embodiment, a CAAC-OS film containing excess oxygen), and is a crystalline oxide semiconductor film. 403 indicates that even if an oxygen deficiency occurs, it contains excess oxygen (preferably excess oxygen than the stoichiometric composition ratio) in the film, so that the excess oxygen acts on the defective part and immediately replenishes the defective part. Can be.

Therefore, by using the crystalline oxide semiconductor film 403 for the transistor 440, the variation in the threshold voltage Vth and the shift ΔVth of the threshold voltage due to oxygen deficiency can be reduced.

The temperature of the heat treatment which crystallizes at least a part of the amorphous oxide semiconductor film 443 is 300 ° C or more and 700 ° C or less, preferably 450 ° C or more and 650 ° C or less, more preferably 500 ° C or more, 550 ° C or more It is done.

For example, a board | substrate is introduce | transduced into the electric furnace which is one of heat processing apparatuses, and heat processing for 1 hour is performed at 450 degreeC under oxygen atmosphere with respect to an oxide semiconductor film.

In the crystalline oxide semiconductor film 403 which has become highly purified and supplemented with oxygen deficiency, impurities such as hydrogen and water are sufficiently removed, and the hydrogen concentration in the crystalline oxide semiconductor film 403 is 5 × 10 19 / cm 3 or less. Preferably, it is 5 * 10 <18> / cm <3> or less.

In this crystalline oxide semiconductor film 403, there are very few carriers (close to zero), and the carrier concentration is less than 1x10 14 / cm 3, preferably less than 1x10 12 / cm 3, more preferably 1x10. Less than 11 / cm 3.

Through the above steps, the transistor 440 is formed (see FIG. 5F). The transistor 440 is a transistor having a crystalline oxide semiconductor film that is highly purified and contains an excess of oxygen to compensate for oxygen deficiency. Therefore, the transistor 440 is suppressed from fluctuation in electrical characteristics and is electrically stable.

The transistor 440 using the crystalline oxide semiconductor film 403 which has been made high using the present embodiment and has an excessive amount of oxygen to supplement the oxygen deficiency has a current value in the off state (off current Value) at room temperature per 1 μm of channel width at 100 zA / μm (1zA (p-ampere) is 1 × 10 −21 A) or less, preferably 10 zA / μm or less, more preferably 1 zA / μm or less, still more preferably Can be made low to a level below 100yA / µm.

As described above, a semiconductor device using an oxide semiconductor having stable electrical characteristics can be provided. Therefore, a highly reliable semiconductor device can be provided.

Embodiment 6

In this embodiment, another embodiment of the semiconductor device and the manufacturing method of the semiconductor device will be described with reference to FIG. 6. The part and the process which have the same part or the same function as the said embodiment can be performed similarly to the said embodiment, and repeated description is abbreviate | omitted. In addition, detailed description of the same location is abbreviate | omitted.

In this embodiment, in the method of manufacturing a semiconductor device according to the disclosed invention, an example is described in which an oxygen introduction step into an amorphous oxide semiconductor film is performed through a gate insulating film after the gate electrode layer is formed.

6A to 6E show an example of the manufacturing method of the transistor 440 in the present embodiment.

First, an insulating film 436 is formed on the substrate 400. An amorphous oxide semiconductor film 492 is formed over the insulating film 436. A gate insulating film 442 is formed to cover the amorphous oxide semiconductor film 492.

The gate electrode layer 401 is formed over the gate insulating film 442 (see FIG. 6A).

The amorphous oxide semiconductor film 492 may also be subjected to a heat treatment for removing (dehydrating or dehydrogenating) excess hydrogen (including water and hydroxyl groups).

Next, oxygen 431 (including at least one of oxygen radicals, oxygen atoms, and oxygen ions) is introduced into the amorphous oxide semiconductor film 492, and oxygen is supplied to the amorphous oxide semiconductor film 492. .

In the present embodiment, after the gate electrode layer 401 is formed, oxygen 431 is injected into the amorphous oxide semiconductor film 492 through the gate insulating film 442 by the ion implantation method. By the implantation process of oxygen 431, the amorphous oxide semiconductor film 492 has an amorphous oxide semiconductor film 443 in which an oxide semiconductor contains a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state. (See FIG. 6B).

When oxygen is introduced, the gate electrode layer 401 may not be directly introduced into the region of the amorphous oxide semiconductor film 492 in which the gate electrode layer 401 becomes a mask and the gate electrode layer 401 overlaps. Since the width of N is small (for example, submicro level), the gate electrode layer 401 overlaps oxygen introduced into the amorphous oxide semiconductor film 443 by heat treatment for crystallization of the amorphous oxide semiconductor film 443. It can also diffuse into the region of the amorphous oxide semiconductor film 443.

The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 443.

Sidewall insulating layers 412a and 412b and sidewall insulating layers 402 having sidewall structures are formed on the side surfaces of the gate electrode layer 401.

The gate insulating layer 402 may be formed by etching the gate insulating layer 442 using the gate electrode layer 401 and the sidewall insulating layers 412a and 412b as a mask.

Subsequently, a conductive film serving as a source electrode layer and a drain electrode layer (including wiring formed in the same layer) is formed on a portion of the sidewall insulating layers 412a and 412b and the amorphous oxide semiconductor film 443.

A resist mask is formed on the conductive film by a photolithography step, and selectively etched to form the source electrode layer 405a and the drain electrode layer 405b, and then the resist mask is removed (see Fig. 6C).

Next, an insulating film 407 is formed over the gate electrode layer 401, the sidewall insulating layers 412a and 412b, the source electrode layer 405a, and the drain electrode layer 405b (see FIG. 6D). Although the insulating film 407 may be a single layer or lamination, it is set as the structure containing an aluminum oxide film.

In this embodiment, an aluminum oxide film having a thickness of 100 nm is formed as the insulating film 407 by using a sputtering method.

Next, the amorphous oxide semiconductor film 443 is subjected to heat treatment to crystallize at least a part of the amorphous oxide semiconductor film 443 to form a crystalline oxide semiconductor film 403. By this heat treatment, oxygen diffuses through the entire amorphous oxide semiconductor film 443, and oxygen is supplied over the whole film.

In this embodiment, the crystalline oxide semiconductor film 403 is formed as the crystalline oxide semiconductor film 403 including a crystal having a c-axis approximately perpendicular to the surface.

The aluminum oxide film formed as the insulating film 407 on the amorphous oxide semiconductor film 443 has a high blocking effect (block effect) that does not allow the film to pass through both impurities such as hydrogen and water and oxygen.

Therefore, the aluminum oxide film is mixed in the oxide semiconductor film (amorphous oxide semiconductor film 443 and the crystalline oxide semiconductor film 403) of impurities such as hydrogen and moisture, which are factors of variation during and after the fabrication process, And a protective film which prevents emission of oxygen semiconductor films (amorphous oxide semiconductor film 443 and crystalline oxide semiconductor film 403) which are main component materials constituting the oxide semiconductor.

Since the heat treatment for crystallizing the amorphous oxide semiconductor film 443 is performed in a state where the amorphous oxide semiconductor film 443 is covered by the aluminum oxide film formed as the insulating film 407, the amorphous oxide semiconductor is subjected to heat treatment for crystallization. The release of oxygen from the film 443 can be prevented. Therefore, the obtained crystalline oxide semiconductor film 403 maintains the amount of oxygen contained in the amorphous oxide semiconductor film 443 and includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. I can do it.

Therefore, the crystalline oxide semiconductor film 403 formed is of high purity because the incorporation of impurities such as hydrogen and moisture and the release of excess oxygen are prevented by the aluminum oxide film, so that the oxide semiconductor is in a crystalline state. Regarding the stoichiometric composition ratio in the above, the oxygen content includes an excess region.

In the crystalline oxide semiconductor film 403, oxygen vacancies exist at a place where oxygen is released. An oxide semiconductor which does not contain oxygen excessively cannot supplement the deficiency with other oxygen even if an oxygen deficiency occurs. However, the crystalline oxide semiconductor film 403 of one embodiment of the disclosed invention is a film containing excessive oxygen (in this embodiment, a CAAC-OS film containing excess oxygen), and is a crystalline oxide semiconductor film. 403 indicates that even if an oxygen deficiency occurs, it contains excess oxygen (preferably excess oxygen than the stoichiometric composition ratio) in the film, so that the excess oxygen acts on the defective part and immediately replenishes the defective part. Can be.

Therefore, by using the crystalline oxide semiconductor film 403 for the transistor 440, the variation in the threshold voltage Vth and the shift ΔVth of the threshold voltage due to oxygen deficiency can be reduced.

The transistor 440 is formed by the above process (see FIG. 6E). The transistor 440 is a transistor having a crystalline oxide semiconductor film that is highly purified and contains an excess of oxygen to compensate for oxygen deficiency. Therefore, the transistor 440 is suppressed from fluctuation in electrical characteristics and is electrically stable.

The transistor 440 using the crystalline oxide semiconductor film 403 which has been made high using the present embodiment and has an excessive amount of oxygen to supplement the oxygen deficiency has a current value in the off state (off current Value) at room temperature per 1 μm of channel width at 100 zA / μm (1zA (p-ampere) is 1 × 10 −21 A) or less, preferably 10 zA / μm or less, more preferably 1 zA / μm or less, still more preferably Can be made low to a level below 100yA / µm.

As described above, a semiconductor device using an oxide semiconductor having stable electrical characteristics can be provided. Therefore, a highly reliable semiconductor device can be provided.

(Embodiment 7)

In this embodiment, another embodiment of the semiconductor device and the manufacturing method of the semiconductor device will be described with reference to FIG. 7. The part and the process which have the same part or the same function as the said embodiment can be performed similarly to the said embodiment, and repeated description is abbreviate | omitted. In addition, detailed description of the same location is abbreviate | omitted.

In this embodiment, in the manufacturing method of the semiconductor device which concerns on this invention, the example which performs the oxygen introduction process to an amorphous oxide semiconductor film through the insulating film formed on a transistor is shown.

7A to 7E show an example of the manufacturing method of the transistor 420 in the present embodiment.

First, an insulating film 436 is formed on the substrate 400. An amorphous oxide semiconductor film 492 is formed over the insulating film 436. A gate insulating film 442 is formed to cover the amorphous oxide semiconductor film 492.

The gate electrode layer 401 is formed over the gate insulating film 442 (see FIG. 7A).

In addition, in this embodiment, the example which uses the gate insulating film 442 formed as a continuous film without forming the side wall insulating layer of a side wall structure, and processing a gate insulating film also in island shape is shown.

The amorphous oxide semiconductor film 492 may be subjected to a heat treatment for removing (dehydrating or dehydrogenating) excess hydrogen (including water and hydroxyl groups).

Next, an insulating film 407 is formed over the gate insulating film 442 and the gate electrode layer 401 (see FIG. 7B). Although the insulating film 407 may be a single layer or lamination, it is set as the structure containing an aluminum oxide film.

In this embodiment, an aluminum oxide film having a thickness of 100 nm is formed as the insulating film 407 by using a sputtering method.

Next, oxygen 431 (including at least one of oxygen radicals, oxygen atoms, and oxygen ions) is introduced into the amorphous oxide semiconductor film 492, and oxygen is supplied to the amorphous oxide semiconductor film 492. .

In the present embodiment, after the insulating film 407 is formed, oxygen 431 is injected into the amorphous oxide semiconductor film 492 through the gate insulating film 442 and the insulating film 407 by an ion implantation method. By the implantation process of oxygen 431, the amorphous oxide semiconductor film 492 has an amorphous oxide semiconductor film 443 in which an oxide semiconductor contains a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state. (See FIG. 7C).

When oxygen is introduced, the gate electrode layer 401 may not be directly introduced into the region of the amorphous oxide semiconductor film 492 in which the gate electrode layer 401 becomes a mask and the gate electrode layer 401 overlaps. Since the width of is narrow (for example, 0.35 탆), the gate electrode layer 401 overlaps oxygen introduced into the amorphous oxide semiconductor film 443 by heat treatment for crystallization of the amorphous oxide semiconductor film 443. It can also diffuse into the region of the amorphous oxide semiconductor film 443.

The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 443.

Next, the amorphous oxide semiconductor film 443 is subjected to heat treatment to crystallize at least a portion of the amorphous oxide semiconductor film 443 to form a crystalline oxide semiconductor film 403 (see FIG. 7D). In addition, oxygen is diffused into the entire amorphous oxide semiconductor film 443 by the heat treatment, and oxygen is supplied through the entire film.

In this embodiment, the crystalline oxide semiconductor film 403 is formed as the crystalline oxide semiconductor film 403 including a crystal having a c-axis approximately perpendicular to the surface.

The aluminum oxide film formed as the insulating film 407 on the amorphous oxide semiconductor film 443 has a high blocking effect (block effect) that does not allow the film to pass through both impurities such as hydrogen and water and oxygen.

Therefore, the aluminum oxide film is mixed in the oxide semiconductor film (amorphous oxide semiconductor film 443 and the crystalline oxide semiconductor film 403) of impurities such as hydrogen and moisture, which are factors of variation during and after the fabrication process, And a protective film which prevents emission of oxygen semiconductor films (amorphous oxide semiconductor film 443 and crystalline oxide semiconductor film 403) which are main component materials constituting the oxide semiconductor.

Since the heat treatment for crystallizing the amorphous oxide semiconductor film 443 is performed in a state where the amorphous oxide semiconductor film 443 is covered by the aluminum oxide film formed as the insulating film 407, the amorphous oxide semiconductor is subjected to heat treatment for crystallization. The release of oxygen from the film 443 can be prevented. Therefore, the obtained crystalline oxide semiconductor film 403 maintains the amount of oxygen contained in the amorphous oxide semiconductor film 443 and includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. I can do it.

Therefore, the crystalline oxide semiconductor film 403 formed is because the aluminum oxide film prevents the incorporation of impurities such as hydrogen and moisture, and the release of excess oxygen, by the aluminum oxide film, so that the oxide semiconductor is in a crystalline state. Regarding the stoichiometric composition ratio in the above, the oxygen content includes an excess region.

In the crystalline oxide semiconductor film 403, oxygen vacancies exist at a place where oxygen is released. An oxide semiconductor which does not contain oxygen excessively cannot supplement the deficiency with other oxygen even if an oxygen deficiency occurs. However, the crystalline oxide semiconductor film 403 of one embodiment of the disclosed invention is a film containing excessive oxygen (in this embodiment, a CAAC-OS film containing excess oxygen), and is a crystalline oxide semiconductor film. 403 indicates that even if an oxygen deficiency occurs, it contains excess oxygen (preferably excess oxygen than the stoichiometric composition ratio) in the film, so that the excess oxygen acts on the defective part and immediately replenishes the defective part. Can be.

Therefore, by using the crystalline oxide semiconductor film 403 for the transistor 420, the variation in the threshold voltage Vth and the shift ΔVth of the threshold voltage due to the oxygen deficiency can be reduced.

In addition, in order to reduce the surface unevenness attributable to the transistor, a planarization insulating film may be formed. As the planarization insulating film, organic materials such as polyimide, acryl and benzocyclobutene resin can be used. In addition to the above organic materials, low dielectric constant materials (low-k materials) and the like can be used. In addition, a planarization insulating film may be formed by stacking a plurality of insulating films formed of these materials.

In this embodiment, the planarization insulating film 415 is formed on the insulating film 407. In addition, an opening reaching the crystalline oxide semiconductor film 403 is formed in the gate insulating film 442, the insulating film 407, and the planarization insulating film 415, and the opening is electrically connected to the crystalline oxide semiconductor film 403. The source electrode layer 405a and the drain electrode layer 405b are formed.

The transistor 420 is formed by the above process (see FIG. 7E). The transistor 420 is a transistor having a crystalline oxide semiconductor film that is highly purified and contains an excess of oxygen to compensate for oxygen deficiency. Therefore, the transistor 420 is suppressed from fluctuation in electrical characteristics and is electrically stable.

In the case where the insulating film 407 is laminated, an inorganic insulating film such as a silicon oxide film, a silicon oxynitride film, an aluminum oxynitride film, or a gallium oxide film can be typically used in addition to the aluminum oxide film. In the transistor 420 in FIG. 10C, the transistor 420a is shown as an example in which the insulating film 407 has a stacked structure of the insulating film 407a and the insulating film 407b.

As shown in Fig. 10C, an insulating film 407a is formed over the gate insulating film 402 and the gate electrode layer 401, and an insulating film 407b is formed over the insulating film 407a. For example, in this embodiment, as the insulating film 407a, a silicon oxide film containing a region in which oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state is used, and the insulating film 407b is used. As the aluminum oxide film is used.

When the insulating film 407 is a laminated structure of the insulating films 407a and 407b, the oxygen introduction step into the amorphous oxide semiconductor film 492 can be performed through the insulating films 407a and 407b to be laminated.

The transistor 420 using the crystalline oxide semiconductor film 403 which has been made high using the present embodiment and has an excessive amount of oxygen to compensate for oxygen deficiency has a current value in the off state (off current Value) at room temperature per 1 μm of channel width at 100 zA / μm (1zA (p-ampere) is 1 × 10 −21 A) or less, preferably 10 zA / μm or less, more preferably 1 zA / μm or less, still more preferably Can be made low to a level below 100yA / µm.

As described above, a semiconductor device using an oxide semiconductor having stable electrical characteristics can be provided. Therefore, a highly reliable semiconductor device can be provided.

Embodiment 8

In this embodiment, another embodiment of the semiconductor device and the manufacturing method of the semiconductor device will be described with reference to FIG. 8. The part and the process which have the same part or the same function as the said embodiment can be performed similarly to the said embodiment, and repeated description is abbreviate | omitted. In addition, detailed description of the same location is abbreviate | omitted.

In this embodiment, the example of the manufacturing method of the transistor from which the connection structure of Embodiment 5, the source electrode layer, the drain electrode layer, and a crystalline oxide semiconductor film differ is shown.

8A to 8F show an example of the manufacturing method of the transistor 450 in the present embodiment.

First, an insulating film 436 is formed on the substrate 400.

Subsequently, a conductive film serving as a source electrode layer and a drain electrode layer (including a wiring formed from the same layer as this) is formed over the insulating film 436.

A resist mask is formed on the conductive film by a photolithography step, and selectively etched to form the source electrode layer 405a and the drain electrode layer 405b, and then the resist mask is removed (see Fig. 8A).

An amorphous oxide semiconductor film 492 is formed over the insulating film 436, the source electrode layer 405a, and the drain electrode layer 405b (see FIG. 8B). A gate insulating film 402 is formed to cover the amorphous oxide semiconductor film 492 (see FIG. 8C).

The amorphous oxide semiconductor film 492 may also be subjected to a heat treatment for removing (dehydrating or dehydrogenating) excess hydrogen (including water and hydroxyl groups).

Next, oxygen 431 (including at least one of oxygen radicals, oxygen atoms, and oxygen ions) is introduced into the amorphous oxide semiconductor film 492 to supply oxygen to the amorphous oxide semiconductor film 492.

In this embodiment, oxygen 431 is injected into the amorphous oxide semiconductor film 492 through the gate insulating film 402 by the ion implantation method. By the implantation process of oxygen 431, the amorphous oxide semiconductor film 492 has an amorphous oxide semiconductor film 443 in which an oxide semiconductor contains a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state. (See FIG. 8D).

The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 443.

The gate electrode layer 401 is formed on the gate insulating film 402.

In this embodiment, although the side wall insulating layer of a side wall structure is not formed in the side surface of the gate electrode layer 401, as shown in Embodiment 5, the side wall insulating layer of a side wall structure is formed and a gate insulating film is shown. 402 may be processed into an island shape.

Next, an insulating film 407 is formed over the gate insulating film 402 and the gate electrode layer 401 (see FIG. 8E). Although the insulating film 407 may be a single layer or lamination, it is set as the structure containing an aluminum oxide film.

In this embodiment, an aluminum oxide film having a thickness of 100 nm is formed as the insulating film 407 by using a sputtering method.

Next, the amorphous oxide semiconductor film 443 is subjected to a heat treatment to crystallize at least a portion of the amorphous oxide semiconductor film 443 to form a crystalline oxide semiconductor film 403.

In this embodiment, the crystalline oxide semiconductor film 403 is formed as the crystalline oxide semiconductor film 403 including a crystal having a c-axis approximately perpendicular to the surface.

The aluminum oxide film formed as the insulating film 407 on the amorphous oxide semiconductor film 443 has a high blocking effect (block effect) that does not allow the film to pass through both impurities such as hydrogen and water and oxygen.

Therefore, the aluminum oxide film is mixed in the oxide semiconductor film (amorphous oxide semiconductor film 443 and the crystalline oxide semiconductor film 403) of impurities such as hydrogen and moisture, which are factors of variation during and after the fabrication process, And a protective film which prevents emission of oxygen semiconductor films (amorphous oxide semiconductor film 443 and crystalline oxide semiconductor film 403) which are main component materials constituting the oxide semiconductor.

Since the heat treatment for crystallizing the amorphous oxide semiconductor film 443 is performed in a state where the amorphous oxide semiconductor film 443 is covered by the aluminum oxide film formed as the insulating film 407, the amorphous oxide semiconductor is subjected to heat treatment for crystallization. The release of oxygen from the film 443 can be prevented. Therefore, the obtained crystalline oxide semiconductor film 403 maintains the amount of oxygen contained in the amorphous oxide semiconductor film 443 and includes a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. I can do it.

Therefore, the crystalline oxide semiconductor film 403 formed is of high purity because the incorporation of impurities such as hydrogen and moisture and the release of excess oxygen are prevented by the aluminum oxide film, so that the oxide semiconductor is in a crystalline state. Regarding the stoichiometric composition ratio in the above, the oxygen content includes an excess region.

In the crystalline oxide semiconductor film 403, oxygen vacancies exist at a place where oxygen is released. An oxide semiconductor which does not contain oxygen excessively cannot supplement the deficiency with other oxygen even if an oxygen deficiency occurs. However, the crystalline oxide semiconductor film 403 of one embodiment of the disclosed invention is a film containing excessive oxygen (in this embodiment, a CAAC-OS film containing excess oxygen), and is a crystalline oxide semiconductor film. 403 indicates that even if an oxygen deficiency occurs, by containing excess oxygen (preferably excess oxygen than the stoichiometric composition ratio) in the film, the excess oxygen acts on the defective part and can immediately replenish the defective part with oxygen. have.

Therefore, by using the crystalline oxide semiconductor film 403 for the transistor 450, the variation in the threshold voltage Vth and the shift ΔVth of the threshold voltage due to the oxygen deficiency can be reduced.

In the case where the insulating film 407 is laminated, an inorganic insulating film such as a silicon oxide film, a silicon oxynitride film, an aluminum oxynitride film, or a gallium oxide film can be typically used in addition to the aluminum oxide film. In the transistor 450 in FIG. 10D, the transistor 450a is shown as an example in which the insulating film 407 has a stacked structure of the insulating film 407a and the insulating film 407b.

As shown in Fig. 10D, an insulating film 407a is formed over the gate insulating film 402 and the gate electrode layer 401, and an insulating film 407b is formed over the insulating film 407a. For example, in the present embodiment, the insulating film 407a is used as the insulating film 407b by using a silicon oxide film containing a region in which oxygen content is excessive with respect to the stoichiometric composition ratio in the silicon oxide crystal state. An aluminum oxide film is used.

The transistor 450 is formed by the above process (see FIG. 8F). The transistor 450 is a transistor having a crystalline oxide semiconductor film that is highly purified and contains an excess of oxygen to compensate for oxygen deficiency. Therefore, the transistor 450 is suppressed from fluctuation in electrical characteristics and is electrically stable.

The transistor 450 using the crystalline oxide semiconductor film 403 which has been made high using the present embodiment and has an excessive amount of oxygen to supplement the oxygen deficiency has a current value in the off state (off current Value) at room temperature per 1 μm of channel width at 100 zA / μm (1zA (p-ampere) is 1 × 10 −21 A) or less, preferably 10 zA / μm or less, more preferably 1 zA / μm or less, still more preferably Can be made low to a level below 100yA / µm.

As described above, a semiconductor device using an oxide semiconductor having stable electrical characteristics can be provided. Therefore, a highly reliable semiconductor device can be provided.

(Embodiment 9)

In this embodiment, another embodiment of the manufacturing method of the semiconductor device will be described. The part and the process which have the same part or the same function as the said embodiment can be performed similarly to the said embodiment, and repeated description is abbreviate | omitted. In addition, detailed description of the same location is abbreviate | omitted.

In addition, in this embodiment, in the manufacturing process of the transistor 450 shown in Embodiment 8, the example of the applicable oxygen introduction process is shown using the transistor 450c.

9A illustrates an example in which oxygen 431 is introduced directly into the amorphous oxide semiconductor film 492 after the process of FIG. 8B. By the introduction process of the oxygen 431, the amorphous oxide semiconductor film 492 has an amorphous oxide semiconductor film 443 in which an oxide semiconductor contains a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state. ) The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 443. In addition, as shown in FIG. 9A, when oxygen is directly introduced into the exposed amorphous oxide semiconductor film 492, a plasma treatment can be used.

In the transistor that can be produced by one embodiment of the present invention, the positional relationship between the gate electrode layer 401, the source electrode layer 405a, and the drain electrode layer 405b does not overlap with the gate insulating film 402 interposed therebetween. It may be formed without, or may be partially overlapped.

For example, in the eighth embodiment, the transistor 450 illustrated in FIG. 8 includes the source electrode layer 405a, the drain electrode layer 405b, the gate electrode layer 401, the gate insulating film 402, and the crystalline oxide. It is an example of a structure which partially overlaps through the semiconductor film 403.

In the present embodiment, the transistor 450c illustrated in FIGS. 9B and 9C includes a source electrode layer 405a, a drain electrode layer 405b, a gate electrode layer 401, a gate insulating film 402, and a crystalline oxide semiconductor. It is an example of the structure which does not overlap through the film | membrane 403 through it.

9B illustrates an example in which oxygen 431 is introduced through the gate insulating film 402 to the amorphous oxide semiconductor film 492 after the gate electrode layer 401 is formed over the gate insulating film 402. By the introduction process of the oxygen 431, the amorphous oxide semiconductor film 492 has an amorphous oxide semiconductor film 443 in which an oxide semiconductor contains a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state. ) The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 443.

In FIG. 9C, after the insulating film 407 is formed over the gate insulating film 402 and the gate electrode layer 401, oxygen 431 is passed through the gate insulating film 402 and the insulating film 407 through the amorphous oxide semiconductor film 492. It is an example to introduce. By the introduction process of the oxygen 431, the amorphous oxide semiconductor film 492 has an amorphous oxide semiconductor film 443 in which an oxide semiconductor contains a region in which the oxygen content is excessive with respect to the stoichiometric composition ratio in the crystal state. ) The supplied oxygen 431 can compensate for the oxygen deficiency present in the amorphous oxide semiconductor film 443.

9B and 9C, when the introduction process of oxygen 431 into the amorphous oxide semiconductor film 492 is performed after formation of the gate insulating film 402 and the gate electrode layer 401, the gate electrode layer 401 and the source When the electrode layer 405a and the drain electrode layer 405b do not overlap, oxygen to the amorphous oxide semiconductor film 492 positioned between the gate electrode layer 401 and the source electrode layer 405a and the drain electrode layer 405b ( Introduction of 431 can be performed relatively easily.

In this manner, the step of introducing oxygen into the crystalline oxide semiconductor film may be any one after performing dehydration or dehydrogenation treatment, and is not particularly limited. The oxygen may be introduced into the oxide semiconductor film subjected to the dehydration or dehydrogenation treatment a plurality of times.

The transistor produced by the above process is a transistor which has high purity and contains the crystalline oxide semiconductor film which contains the oxygen which supplements oxygen deficiency excessively. Therefore, the transistor is suppressed from fluctuation in electrical characteristics and is electrically stable.

A semiconductor device using an oxide semiconductor having stable electrical characteristics can be provided. Therefore, a highly reliable semiconductor device can be provided.

This embodiment can be implemented in appropriate combination with any of the other embodiments.

(Embodiment 10)

In this embodiment, another embodiment of the semiconductor device and the manufacturing method of the semiconductor device will be described with reference to FIG. 11. The part and the process which have the same part or the same function as the said embodiment can be performed similarly to the said embodiment, and repeated description is abbreviate | omitted. In addition, detailed description of the same location is abbreviate | omitted.

In this embodiment, in the method of manufacturing a semiconductor device according to the disclosed invention, it is an example of forming an impurity region functioning as a source region and a drain region in a crystalline oxide semiconductor film. The impurity region functioning as the source region and the drain region can be formed by introducing an impurity (also referred to as a dopant) that changes the conductivity to the crystalline oxide semiconductor film.

The concentration of the dopant in the impurity region functioning as the source region and the drain region is preferably 5 × 10 18 / cm 3 or more and 1 × 10 22 / cm 3 or less.

The dopant to be introduced is a group 15 element and boron, and specifically, at least one selected from phosphorus, arsenic, antimony and boron. As the method of introducing the dopant into the crystalline oxide semiconductor film, an ion doping method or an ion implantation method can be used.

When the dopant is introduced by the ion doping method or the ion implantation method, the substrate may be heated.

In addition, the process which introduce | transduces a dopant into a crystalline oxide semiconductor film may be performed in multiple times, and multiple types of dopant may be used.

The impurity region into which the dopant is introduced may be partially amorphous by the introduction of the dopant. In this case, crystallinity can be restored by performing heat treatment after introduction of the dopant.

In the transistor 440 shown in Embodiment 5 or Embodiment 6 in FIG. 11A, the transistor 440b having the impurity regions 404a and 404b formed as a source region or a drain region in the crystalline oxide semiconductor film 403. Shows an example. The impurity regions 404a and 404b are formed on the crystalline oxide semiconductor film 403 before the source electrode layer 405a and the drain electrode layer 405b are formed using the gate electrode layer 401 and the sidewall insulating layers 412a and 412b as masks. It can form by introducing a dopant.

11B shows an example of the transistor 420b in which the impurity regions 404a and 404b are formed in the crystalline oxide semiconductor film 403 as a source region or a drain region. do. The impurity regions 404a and 404b can be formed by introducing a dopant into the crystalline oxide semiconductor film 403 using the gate electrode layer 401 as a mask.

11C shows an example of the transistor 450b in which the impurity regions 404a and 404b are formed in the crystalline oxide semiconductor film 403 as a source region or a drain region. do. The impurity regions 404a and 404b can be formed by introducing a dopant into the crystalline oxide semiconductor film 403 using the gate electrode layer 401 as a mask.

By forming an impurity region functioning as a source region or a drain region, the electric field applied to the channel formation region formed between the impurity regions can be relaxed. In addition, by electrically connecting the crystalline oxide semiconductor film and the electrode layer in the impurity region, the contact resistance between the crystalline oxide semiconductor film and the electrode layer can be reduced. Therefore, the electrical characteristics of the transistor can be improved.

This embodiment can be implemented in appropriate combination with any of the other embodiments.

(Embodiment 11)

The semiconductor device (also called a display device) which has a display function can be manufactured using the transistor which showed an example in any one of Embodiment 1-10. In addition, part or all of the driving circuit including the transistor may be integrally formed on the same substrate as the pixel portion to form a system on panel.

In FIG. 13A, a seal member 4005 is formed to surround the pixel portion 4002 formed on the first substrate 4001, and is sealed by the second substrate 4006. In FIG. 13A, a scan line driver circuit 4004 and a signal line driver formed of a single crystal semiconductor film or a polycrystalline semiconductor film on a separately prepared substrate in a region different from the region surrounded by the seal member 4005 on the first substrate 4001. The circuit 4003 is mounted. In addition, various signals and potentials given to the separately formed signal line driver circuit 4003 and the scan line driver circuit 4004 or the pixel portion 4002 are supplied from FPC (Flexible printed circuit) 4018a and 4018b.

13B and 13C, a seal member 4005 is formed so as to surround the pixel portion 4002 formed on the first substrate 4001 and the scanning line driver circuit 4004. A second substrate 4006 is formed over the pixel portion 4002 and the scan line driver circuit 4004. Therefore, the pixel portion 4002 and the scanning line driver circuit 4004 are sealed together with the display element by the first substrate 4001, the seal member 4005, and the second substrate 4006. 13B and 13C, a signal line driver circuit 4003 formed of a single crystal semiconductor film or a polycrystalline semiconductor film on a substrate separately prepared in a region different from the region surrounded by the seal member 4005 on the first substrate 4001. Is mounted. In FIGS. 13B and 13C, various signals and potentials supplied to the separately formed signal line driver circuit 4003, the scan line driver circuit 4004, or the pixel portion 4002 are supplied from the FPC 4018.

13B and 13C show an example in which the signal line driver circuit 4003 is separately formed and mounted on the first substrate 4001, but is not limited to this configuration. The scan line driver circuit may be separately formed and mounted, or only a part of the signal line driver circuit or a part of the scan line driver circuit may be separately formed and mounted.

In addition, the connection method of the separately formed drive circuit is not specifically limited, A COG (Chip On Glass) method, a wire bonding method, the Tape Automated Bonding (TAB) method, etc. can be used. FIG. 13A is an example in which the signal line driver circuit 4003 and the scan line driver circuit 4004 are mounted by the COG method. FIG. 13B is an example in which the signal line driver circuit 4003 is mounted by the COG method. Is an example of mounting the signal line driver circuit 4003 by the TAB method.

The display device also includes a panel in which the display element is encapsulated, and a module in a state in which an IC including a controller is mounted on the panel.

In addition, the display apparatus in this specification refers to an image display device, a display device, or a light source (including an illumination device). In addition, a connector, for example, a module with an FPC or TAB tape or TCP, a module with a printed wiring board formed at the end of the TAB tape or TCP, or a module in which an IC (integrated circuit) is directly mounted by a COG method on a display element It is assumed that it is included in the display device.

The pixel portion and the scan line driver circuit formed on the first substrate have a plurality of transistors, and any one of Embodiments 1 to 10 can use the transistor shown as an example.

As a display element formed in a display apparatus, a liquid crystal element (also called liquid crystal display element) and a light emitting element (also called light emitting display element) can be used. The light emitting element includes, in its category, an element whose luminance is controlled by current or voltage, and specifically includes inorganic EL (Electro Luminescence), organic EL, and the like. Further, a display medium in which the contrast is changed by an electrical action such as an electronic ink can also be applied.

One embodiment of the semiconductor device will be described with reference to FIGS. 13 and 14. FIG. 14 is corresponded to sectional drawing in M-N of FIG. 13B.

As shown in FIG. 13 and FIG. 14, the semiconductor device has a connecting terminal electrode 4015 and a terminal electrode 4016, and the connecting terminal electrode 4015 and the terminal electrode 4016 are terminals included in the FPC 4018. And an anisotropic conductive film 4019 are electrically connected to each other.

The connection terminal electrode 4015 is formed of the same conductive film as the first electrode layer 4030, and the terminal electrode 4016 is formed of the same conductive film as the source electrode layer and the drain electrode layer of the transistors 4010 and 4011.

In addition, the pixel portion 4002 and the scanning line driver circuit 4004 formed on the first substrate 4001 include a plurality of transistors. In FIG. 14, the transistor 4010 and the scan line driving included in the pixel portion 4002. The transistor 4011 included in the circuit 4004 is illustrated. In FIG. 14A, an insulating film 4020 and an insulating film 4032 are formed over the transistors 4010 and 4011, and an insulating film 4021 is formed in FIG. 14B. The insulating film 4023 is an insulating film functioning as an underlayer.

As the transistors 4010 and 4011, the transistors described in any one of Embodiments 1 to 10 can be used. In this embodiment, an example in which a transistor having the same structure as the transistor 410 shown in Embodiment 1 is applied.

The transistor 4010 and the transistor 4011 are transistors having a crystalline oxide semiconductor film that is highly purified and contains an excess of oxygen to compensate for oxygen deficiency. Therefore, the transistor 4010 and the transistor 4011 are electrically stable because electrical characteristic variations are suppressed.

Therefore, a highly reliable semiconductor device can be provided as the semiconductor device of this embodiment shown in FIGS. 13 and 14.

In this embodiment, the conductive layer is formed on the insulating film at a position overlapping with the channel formation region of the crystalline oxide semiconductor film of the driver circuit transistor 4011. By forming the conductive layer at a position overlapping with the channel formation region of the crystalline oxide semiconductor film, the amount of change in the threshold voltage of the transistor 4011 before and after the bias-thermal stress test (BT test) can be further reduced. The conductive layer may have the same or different potential as the gate electrode layer of the transistor 4011, and may function as a second gate electrode layer. In addition, the potential of the conductive layer may be GND, 0 V, or a floating state.

The conductive layer also has a function of shielding the external electric field, that is, preventing the external electric field from acting on the interior (circuit section including the transistor) (especially an electrostatic shielding function against static electricity). By the shielding function of the conductive layer, it is possible to prevent the electrical characteristics of the transistor from changing due to the influence of an external electric field such as static electricity.

The transistor 4010 formed in the pixel portion 4002 is electrically connected to the display element and constitutes a display panel. The display element is not particularly limited as long as it can display, and various display elements can be used.

The example of the liquid crystal display device which used the liquid crystal element as a display element in FIG. 14A is shown. In FIG. 14A, the liquid crystal element 4013 that is a display element includes a first electrode layer 4030, a second electrode layer 4031, and a liquid crystal layer 4008. In addition, insulating films 4032 and 4033 functioning as alignment films are formed so as to sandwich the liquid crystal layer 4008. The second electrode layer 4031 is formed on the second substrate 4006 side, and the first electrode layer 4030 and the second electrode layer 4031 are laminated with the liquid crystal layer 4008 interposed therebetween.

4035 is a columnar spacer obtained by selectively etching the insulating film, and is formed to control the film thickness (cell gap) of the liquid crystal layer 4008. In addition, spherical spacers may be used.

As the display element, a thermotropic liquid crystal, a low molecular liquid crystal, a polymer liquid crystal, a polymer dispersed liquid crystal, a ferroelectric liquid crystal, an antiferroelectric liquid crystal, or the like can be used. These liquid crystal materials (liquid crystal composition) show a cholesteric phase, a smectic phase, a cubic phase, a chiral nematic phase, an isotropic phase, etc. according to conditions.

In addition, you may use for the liquid crystal layer 4008 the liquid crystal composition which expresses the blue phase which does not use an oriented film. The blue phase is one of the liquid crystal phases, and when the cholesteric liquid crystal is heated, the blue phase is a phase which is expressed immediately before transition from the cholesteric phase to the isotropic phase. A blue phase can be expressed using the liquid crystal composition which mixed the liquid crystal and a chiral agent. In addition, in order to broaden the temperature range in which a blue phase is expressed, a liquid crystal layer can be formed by adding a polymerizable monomer, a polymerization initiator, etc. to the liquid crystal composition which expresses a blue phase, and stabilizing a polymer. Since the liquid crystal composition which expresses a blue phase has a short response speed and is optically isotropic, an orientation process is unnecessary and a viewing angle dependency is small. In addition, since it is not necessary to form the alignment film, the rubbing treatment is also unnecessary, so that electrostatic breakdown caused by the rubbing treatment can be prevented, and defects or breakage of the liquid crystal display device during the manufacturing process can be reduced. Therefore, it becomes possible to improve productivity of a liquid crystal display device. In the transistor using the oxide semiconductor film, the electrical characteristics of the transistor are significantly changed by the influence of static electricity, which may deviate from the design range. Therefore, it is more effective to use the liquid crystal composition which expresses a blue phase in the liquid crystal display device which has a transistor using an oxide semiconductor film.

The resistivity of the liquid crystal material is 1 × 10 9 Ω · cm or more, preferably 1 × 10 11 Ω · cm or more, and more preferably 1 × 10 12 Ω · cm or more. In addition, the value of the specific resistance in this specification is made into the value measured at 20 degreeC.

The size of the storage capacitor formed in the liquid crystal display device is set so that the charge can be maintained for a predetermined period in consideration of the leak current of the transistor disposed in the pixel portion. The size of the holding capacitor may be set in consideration of the off current of the transistor and the like. By using a transistor having a high purity crystalline oxide semiconductor film, it is sufficient to form a storage capacitor having a size of 1/3 or less, preferably 1/5 or less of the liquid crystal capacitance in each pixel.

The transistor using the highly purified crystalline oxide semiconductor film used in the present embodiment can lower the current value (off current value) in the off state. Therefore, the holding time of an electrical signal such as an image signal can be lengthened, and the recording interval can also be set long in the power-on state. Therefore, since the frequency of the refresh operation can be reduced, the power consumption can be suppressed.

In addition, the transistor using the highly purified crystalline oxide semiconductor film used in the present embodiment can obtain a high speed drive because a relatively high field effect mobility can be obtained. For example, by using such a transistor capable of high-speed driving in a liquid crystal display device, a switching transistor of a pixel portion and a driver transistor for use in a driving circuit portion can be formed on the same substrate. That is, since it is not necessary to use the semiconductor device formed by the silicon wafer etc. as a separate drive circuit, the number of components of a semiconductor device can be reduced. Also, in the pixel portion, by using a transistor capable of high speed driving, a high quality image can be provided.

Liquid crystal display devices include twisted nematic (TN) mode, in-plane-switching (IPS) mode, freted field switching (FSF) mode, symmetrically aligned micro-cell (ASM) mode, optically compensated birefringence (OCB) mode, and FLC. (Ferroelectric Liquid Crystal) mode, AFLC (Anti Ferroelectric Liquid Crystal) mode, and the like can be used.

Moreover, it is good also as a transmission type liquid crystal display device which employ | adopted a normally black liquid crystal display device, for example, a vertical alignment (VA) mode. Some examples of the vertical alignment mode include, but are not limited to, a multi-domain vertical alignment (MVA) mode, a patterned vertical alignment (PVA) mode, an advanced super view (ASV) mode, and the like. Moreover, it is applicable also to VA type liquid crystal display device. VA type liquid crystal display device is a kind of system which controls the arrangement | sequence of the liquid crystal molecule of a liquid crystal display panel. The VA type liquid crystal display device is a system in which liquid crystal molecules are directed perpendicular to the panel surface when no voltage is applied. In addition, a method called multi-domainization or multi-domain design, which is designed to divide a pixel (pixel) into several regions (sub pixels) and to knock down molecules in different directions, can be used.

In the display device, an optical member (optical substrate) such as a black matrix (light shielding layer), a polarizing member, a retardation member, an antireflection member, or the like is appropriately formed. For example, circular polarization by a polarizing substrate and a retardation substrate may be used. Moreover, you may use a backlight, a side light, etc. as a light source.

As the display method in the pixel portion, a progressive method, an interlace method, or the like can be used. In addition, as a color element controlled by a pixel at the time of color display, it is not limited to three colors of RGB (R is red, G is green, B is blue). For example, RGBW (W represents white) or RGB, yellow, cyan, magenta, etc., have added one or more colors. In addition, the size of the display area may be different for each dot of the color element. However, the disclosed invention is not limited to the display device for color display, but can also be applied to the display device for monochrome display.

In addition, as a display element included in the display device, a light emitting element using an electroluminescence can be applied. The light emitting element using the electroluminescence is distinguished by whether the light emitting material is an organic compound or an inorganic compound. In general, the former is called an organic EL element, and the latter is called an inorganic EL element.

By applying a voltage to the light emitting element, the organic EL element is injected with electrons and holes from the pair of electrodes into the layer containing the light emitting organic compound, respectively, and a current flows. And by recombination of these carriers (electrons and holes), the luminescent organic compound forms an excited state and emits light when the excited state returns to the ground state. From this mechanism, such a light emitting element is called a current excitation type light emitting element.

An inorganic EL element is classified into a distributed inorganic EL element and a thin-film inorganic EL element by the element structure. A dispersed inorganic EL device has a light emitting layer in which particles of a light emitting material are dispersed in a binder, and the light emitting mechanism is donor-acceptor recombination type light emission using a donor level and an acceptor level. The thin-film inorganic EL device has a structure in which a light emitting layer is interposed between dielectric layers and between electrodes, and the light emitting mechanism is localized light emission using a cabinet electron transition of metal ions. In addition, it demonstrates using an organic electroluminescent element as a light emitting element here.

In the light emitting element, at least one of the pair of electrodes may be light-transmitting to extract light emission. Then, a transistor and a light emitting element are formed on the substrate, and the upper surface ejection extracts light emission from the surface on the opposite side from the substrate, or the lower surface ejection extracts light emission from the surface on the substrate side. There exists a light emitting element of the double-sided injection structure which extracts light emission, and the light emitting element of any injection structure can be applied.

14B shows an example of a light emitting device using the light emitting element as the display element. The light emitting element 4513 which is a display element is electrically connected to the transistor 4010 formed in the pixel portion 4002. In addition, although the structure of the light emitting element 4513 is a laminated structure of the 1st electrode layer 4030, the electroluminescent layer 4511, and the 2nd electrode layer 4031, it is not limited to the structure shown. The configuration of the light emitting element 4513 can be appropriately changed in accordance with the direction of light to be extracted from the light emitting element 4513 and the like.

The partition wall 4510 is formed using an organic insulating material or an inorganic insulating material. In particular, it is preferable that an opening is formed on the first electrode layer 4030 using a photosensitive resin material, and the side wall of the opening is formed to be an inclined surface formed with a continuous curvature.

The electroluminescent layer 4511 may be comprised of a single layer, or may be comprised so that a some layer may be laminated | stacked.

A protective film may be formed on the second electrode layer 4031 and the partition wall 4510 so that oxygen, hydrogen, moisture, carbon dioxide, and the like do not enter the light emitting element 4513. As the protective film, a silicon nitride film, a silicon nitride oxide film, a DLC film, or the like can be formed. In addition, a filler 4414 is formed and sealed in a space sealed by the first substrate 4001, the second substrate 4006, and the seal member 4005. It is preferable to package (encapsulate) with a protective film (bonding film, an ultraviolet curable resin film, etc.) and a cover material with high airtightness and few degassing so that it may not be exposed to external air in this way.

As the filler 4514, an ultraviolet curable resin or a thermosetting resin can be used in addition to an inert gas such as nitrogen or argon, and PVC (polyvinyl chloride), acrylic, polyimide, epoxy resin, silicone resin, PVB (polyvinyl butyral) ) Or EVA (ethylene vinyl acetate) can be used. For example, nitrogen may be used as the filler.

If necessary, optical films such as polarizing plates or circular polarizing plates (including elliptical polarizing plates), retardation plates (λ / 4 plate and λ / 2 plates) and color filters may be appropriately formed on the emitting surface of the light emitting element. Moreover, you may provide an anti-reflective film in a polarizing plate or a circularly polarizing plate. For example, antiglare treatment can be applied to diffuse the reflected light due to irregularities on the surface, and to reduce glare.

It is also possible to provide an electronic paper for driving the electronic ink as the display device. Electronic paper is also called an electrophoretic display (electrophoretic display), and has the advantage of being easy to read as paper, and having a low power consumption and a thin and light shape compared to other display devices.

The electrophoretic display device can be considered in various forms, but a microcapsule containing a first particle having a positive charge and a second particle having a negative charge is a plurality of microcapsules dispersed in a solvent or a solute. By applying an electric field to the particles, the particles in the microcapsules are moved in opposite directions to display only the color of the particles collected on one side. In addition, a 1st particle or a 2nd particle contains dye and does not move when there is no electric field. In addition, the color of a 1st particle | grain and the color of a 2nd particle | grain shall be different (including colorlessness).

As described above, the electrophoretic display is a display using a so-called dielectric electrophoretic effect, in which a material having a high dielectric constant moves to a high electric field region.

What disperse | distributed the said microcapsule in a solvent is called an electronic ink, and this electronic ink can be printed on the surface of glass, plastic, cloth, paper, etc. Moreover, color display is also possible by using the particle | grains which have a color filter or a pigment | dye.

Further, the first particles and the second particles in the microcapsules are selected from a conductor material, an insulator material, a semiconductor material, a magnetic material, a liquid crystal material, a ferroelectric material, an electroluminescent material, an electrochromic material, and a magnetophoretic material. It is good to use a seed material or these composite materials.

Moreover, the display apparatus which uses the twist ball display system as an electronic paper is also applicable. The twist ball display method is a method of disposing spherical particles divided into white and black between a first electrode layer and a second electrode layer, which are electrode layers used for a display element, of spherical particles in which a potential difference is generated between the first electrode layer and the second electrode layer. It is a method of displaying by controlling a direction.

In addition, in FIG.13 and FIG.14, as a 1st board | substrate 4001 and the 2nd board | substrate 4006, the board | substrate which has flexibility can be used besides a glass substrate, For example, the plastic substrate etc. which have translucency can be used. Can be. As the plastic, a fiberglass-reinforced plastics (FRP) plate, a polyvinyl fluoride (PVF) film, a polyester film or an acrylic resin film can be used. Moreover, if translucent is not necessary, you may use metal substrates (metal films), such as aluminum and stainless steel. For example, the sheet | seat of the structure which interposed aluminum foil between PVF film or a polyester film can also be used.

In this embodiment, an aluminum oxide film is used as the insulating film 4020. The insulating film 4020 can be formed by sputtering or plasma CVD.

The aluminum oxide film formed as the insulating film 4020 on the oxide semiconductor film has a high blocking effect (block effect) that does not transmit the film to both impurities such as hydrogen and moisture and oxygen.

Therefore, the aluminum oxide film prevents the incorporation of impurities, such as hydrogen and moisture, into the oxide semiconductor film during the production process and after the production, and the release of oxygen from the oxide semiconductor film as the main component material constituting the oxide semiconductor. It functions as a protective film to prevent.

The transistor 4010 and the transistor 4011 have a crystalline oxide semiconductor film obtained by crystallizing an amorphous oxide semiconductor film in which the crystalline oxide semiconductor film is made excess of oxygen by an oxygen introduction step. Since the heat treatment for crystallizing the amorphous oxide semiconductor film is performed in a state covered with the aluminum oxide film, it is possible to prevent oxygen from being released from the amorphous oxide semiconductor film by the heat treatment for crystallization. Therefore, the obtained crystalline oxide semiconductor film can hold | maintain the amount of oxygen which an amorphous oxide semiconductor film contains, and it can be set as the film | membrane containing the area | region which oxygen content is excessive with respect to the stoichiometric composition ratio in an oxide semiconductor crystal state.

Therefore, the crystalline oxide semiconductor film formed is of high purity because impurities such as hydrogen and moisture are not mixed, and oxygen content is excessive with respect to the stoichiometric composition ratio of the oxide semiconductor in the crystal state because oxygen release is prevented. It can be set as the film | membrane containing an area | region. Therefore, by using the crystalline oxide semiconductor film for the transistor 4010 and the transistor 4011, the variation in the threshold voltage Vth and the shift ΔVth of the threshold voltage due to oxygen deficiency can be reduced. .

As the insulating film 4021 serving as the planarization insulating film, an organic material having heat resistance, such as acryl, polyimide, benzocyclobutene resin, polyamide, and epoxy, can be used. In addition to the above organic materials, low dielectric constant materials (low-k materials), siloxane resins, PSG (phosphorus glass), BPSG (phosphorus glass) and the like can be used. In addition, an insulating film may be formed by stacking a plurality of insulating films formed of these materials.

The formation method of the insulating film 4021 is not specifically limited, Depending on the material, sputtering method, SOG method, spin coating, dip, spray coating, droplet ejection method (inkjet method, etc.), printing method (screen printing, offset printing, etc.) ), Doctor knife, roll coater, curtain coater, knife coater and the like can be used.

The display device transmits light from a light source or a display element to perform display. Therefore, all the thin films, such as a board | substrate, an insulating film, and a conductive film formed in the pixel part which light transmits, are translucent with respect to the light of the wavelength range of visible light.

In the first electrode layer and the second electrode layer (also referred to as a pixel electrode layer, a common electrode layer, a counter electrode layer, etc.) for applying a voltage to the display element, the light transmittance and reflectivity are determined by the direction of the extraction light, the location where the electrode layer is formed, and the pattern structure of the electrode layer. It is good to choose.

The first electrode layer 4030 and the second electrode layer 4031 are indium oxide containing tungsten oxide, indium zinc oxide containing tungsten oxide, indium oxide containing titanium oxide, indium tin oxide containing titanium oxide, and indium. Conductive materials having light transmissivity, such as tin oxide, indium zinc oxide, indium tin oxide added with silicon oxide, and graphene, can be used.

The first electrode layer 4030 and the second electrode layer 4031 may include tungsten (W), molybdenum (Mo), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), and tantalum (Ta). , Metals such as chromium (Cr), cobalt (Co), nickel (Ni), titanium (Ti), platinum (Pt), aluminum (Al), copper (Cu), silver (Ag), or alloys thereof, or It can form using one or more types from metal nitride.

The first electrode layer 4030 and the second electrode layer 4031 can be formed using a conductive composition containing a conductive polymer (also called a conductive polymer). As the conductive polymer, a so-called π-electron conjugated conductive polymer can be used. For example, the polyaniline or its derivative (s), polypyrrole or its derivative (s), polythiophene or its derivative (s), or the copolymer which consists of two or more types of aniline, pyrrole and thiophene, or its derivative (s), etc. are mentioned.

In addition, since the transistor is easily broken by static electricity or the like, it is preferable to form a protection circuit for driving circuit protection. It is preferable to comprise a protection circuit using a nonlinear element.

By applying the transistor shown in any one of Embodiments 1-10 as mentioned above, the semiconductor device which has various functions can be provided.

(Twelfth Embodiment)

The semiconductor device which has an image sensor function which reads the information of a target object can be manufactured using the transistor which showed an example in any one of Embodiment 1-10.

15A shows an example of a semiconductor device having an image sensor function. 15A is an equivalent circuit of the photosensor, and FIG. 15B is a sectional view showing a part of the photosensor.

In the photodiode 602, one electrode is electrically connected to the photodiode reset signal line 658, and the other electrode is electrically connected to the gate of the transistor 640. In the transistor 640, one of the source or the drain is electrically connected to the photosensor reference signal line 672, and the other of the source or the drain is electrically connected to one of the source or the drain of the transistor 656. The transistor 656 has a gate electrically connected to the gate signal line 659 and the other of the source or the drain to the photosensor output signal line 671.

In the circuit diagram of the present specification, the symbol of the transistor using the oxide semiconductor film is described as "OS" so that it can be clearly identified as a transistor using the oxide semiconductor film. In Fig. 15A, the transistors 640 and 656 can be applied to the transistors shown in Embodiments 1 to 10, and are transistors using a crystalline oxide semiconductor film. In this embodiment, an example in which a transistor having the same structure as the transistor 410 shown in Embodiment 1 is applied.

FIG. 15B is a cross-sectional view of the photodiode 602 and the transistor 640 in the photosensor, and a photodiode 602 and a transistor (functioning as a sensor) on a substrate 601 (TFT substrate) having an insulating surface. 640 is formed. The substrate 613 is formed on the photodiode 602 and the transistor 640 by using an adhesive layer 608.

An insulating film 631, an insulating film 632, an interlayer insulating film 633, and an interlayer insulating film 634 are formed on the transistor 640. The photodiode 602 is formed on the interlayer insulating film 633, between the electrode layer 641 formed on the interlayer insulating film 633, and the electrode layer 642 formed on the interlayer insulating film 634, on the side of the interlayer insulating film 633. The first semiconductor film 606a, the second semiconductor film 606b, and the third semiconductor film 606c are sequentially stacked.

The electrode layer 641 is electrically connected to the conductive layer 643 formed on the interlayer insulating film 634, and the electrode layer 642 is electrically connected to the conductive layer 645 through the electrode layer 641. The conductive layer 645 is electrically connected to the gate electrode layer of the transistor 640, and the photodiode 602 is electrically connected to the transistor 640.

Here, a semiconductor film having a p-type conductivity type as the first semiconductor film 606a, a high resistance semiconductor film (I-type semiconductor film), and a third semiconductor film 606c as the second semiconductor film 606b. The pin type photodiode which laminate | stacks the semiconductor film which has n type conductivity type is illustrated.

The first semiconductor film 606a is a p-type semiconductor film and can be formed of an amorphous silicon film containing an impurity element imparting a p-type. In the formation of the first semiconductor film 606a, a semiconductor material gas containing a group 13 impurity element (for example, boron (B)) is used by plasma CVD. As the semiconductor material gas, silane (SiH 4 ) may be used. Alternatively, Si 2 H 6 , SiH 2 Cl 2 , SiHCl 3 , SiCl 4 , SiF 4, or the like may be used. After the amorphous silicon film containing no impurity element is formed, the impurity element may be introduced into the amorphous silicon film by using a diffusion method or an ion implantation method. The impurity element may be diffused by introducing the impurity element by ion implantation or the like, followed by heating. In this case, as the method of forming the amorphous silicon film, an LPCVD method, a vapor phase growth method, a sputtering method, or the like may be used. It is preferable to form the film thickness of the 1st semiconductor film 606a so that it may become 10 nm or more and 50 nm or less.

The second semiconductor film 606b is an I-type semiconductor film (intrinsic semiconductor film), and is formed of an amorphous silicon film. In forming the second semiconductor film 606b, an amorphous silicon film is formed by a plasma CVD method using a semiconductor material gas. As the semiconductor material gas, silane (SiH 4 ) may be used. Alternatively, Si 2 H 6 , SiH 2 Cl 2 , SiHCl 3 , SiCl 4 , SiF 4, or the like may be used. The second semiconductor film 606b may be formed by the LPCVD method, the vapor phase growth method, the sputtering method, or the like. The film thickness of the second semiconductor film 606b is preferably formed to be 200 nm or more and 1000 nm or less.

The third semiconductor film 606c is an n-type semiconductor film, and is formed of an amorphous silicon film containing an impurity element imparting n-type. For forming the third semiconductor film 606c, a semiconductor material gas containing a group 15 impurity element (for example, phosphorus (P)) is used by plasma CVD. As the semiconductor material gas, silane (SiH 4 ) may be used. Alternatively, Si 2 H 6 , SiH 2 Cl 2 , SiHCl 3 , SiCl 4 , SiF 4, or the like may be used. After the amorphous silicon film containing no impurity element is formed, the impurity element may be introduced into the amorphous silicon film by using a diffusion method or an ion implantation method. The impurity element may be diffused by introducing the impurity element by ion implantation or the like, followed by heating. In this case, as the method of forming the amorphous silicon film, an LPCVD method, a vapor phase growth method, a sputtering method, or the like may be used. The film thickness of the third semiconductor film 606c is preferably formed to be 20 nm or more and 200 nm or less.

In addition, the first semiconductor film 606a, the second semiconductor film 606b, and the third semiconductor film 606c are not amorphous semiconductors, and may be formed using polycrystalline semiconductors, and may be microcrystalline (Semi Amorphous Semiconductor). : SAS)) You may form using a semiconductor.

Microcrystalline semiconductors belong to an intermediate metastable state between amorphous and single crystals in consideration of the free energy of the cast. That is, a semiconductor having a third state that is freely energetically stable, has short-range order and lattice deformation. Columnar or acicular crystals are growing in the normal direction with respect to the substrate surface. The microcrystalline silicon, which is a representative example of the microcrystalline semiconductor, is shifted to the lower wave side than the 520 cm -1 where the Raman spectrum represents single crystal silicon. That is, it is the Raman spectrum of microcrystalline silicon on a peak showing the 520㎝ 480㎝ -1 between -1 and the amorphous silicon indicates a single crystalline silicon. Moreover, in order to terminate unbound water (dangling bond), hydrogen or a halogen is contained at least 1 atomic% or more. Further, by containing rare gas elements such as helium, argon, krypton, and neon to further promote lattice deformation, stability is increased and a good microcrystalline semiconductor film is obtained.

The microcrystalline semiconductor film can be formed by a high frequency plasma CVD method having a frequency of several tens of MHz to several hundred MHz or a microwave plasma CVD apparatus having a frequency of 1 GHz or more. Typically, compounds containing silicon such as SiH 4 , Si 2 H 6 , SiH 2 Cl 2 , SiHCl 3 , SiCl 4 , and SiF 4 can be formed by diluting with hydrogen. In addition to the silicon-containing compound (for example, silicon hydride) and hydrogen, a microcrystalline semiconductor film can be formed by diluting with one or a plurality of rare gas elements selected from helium, argon, krypton, and neon. The flow rate ratio of hydrogen is 5 times or more and 200 times or less, preferably 50 times or more and 150 times or less, and more preferably 100 times with respect to the compound containing silicon (for example, silicon hydride) at this time. Further, in the gas containing silicon, CH 4, C 2 H 6, etc. of the carbide gas, GeH 4, may even incorporate germanium screen gas, such as F 2, such as GeF 4.

In addition, since the mobility of holes generated in the photoelectric effect is smaller than the mobility of electrons, the pin-type photodiode has a better characteristic of making the p-type semiconductor film side the light-receiving surface. Here, the example which converts the light which the photodiode 602 receives from the surface of the board | substrate 601 in which the pin type photodiode is formed into an electrical signal is shown. In addition, since the light from the semiconductor film side having the conductivity type opposite to the semiconductor film side serving as the light receiving surface becomes disturbing light, the electrode layer may be a conductive film having light shielding properties. The n-type semiconductor film side can also be used as the light receiving surface.

As the insulating film 632, the interlayer insulating film 633, and the interlayer insulating film 634, an insulating material is used, and depending on the material, the sputtering method, the plasma CVD method, the SOG method, the spin coat, the dip, the spray coating, and the droplet discharging method (Inkjet method, etc.), printing method (screen printing, offset printing, etc.), a doctor knife, a roll coater, a curtain coater, a knife coater, etc. can be formed.

In this embodiment, an aluminum oxide film is used as the insulating film 631. The insulating film 631 can be formed by sputtering or plasma CVD.

The aluminum oxide film formed as the insulating film 631 on the oxide semiconductor film has a high blocking effect (block effect) that does not transmit the film to both impurities such as hydrogen and moisture and oxygen.

Therefore, the aluminum oxide film prevents the incorporation of impurities, such as hydrogen and moisture, into the oxide semiconductor film during the production process and after the production, and the release of oxygen from the oxide semiconductor film as the main component material constituting the oxide semiconductor. It functions as a protective film to prevent.

In the present embodiment, the transistor 640 has a crystalline oxide semiconductor film obtained by crystallizing an amorphous oxide semiconductor film in which oxygen is excessively introduced. Since the heat treatment for crystallizing the amorphous oxide semiconductor film is performed in a state covered with the aluminum oxide film, it is possible to prevent oxygen from being released from the amorphous oxide semiconductor film by the heat treatment for crystallization. Therefore, the obtained crystalline oxide semiconductor film can hold | maintain the amount of oxygen which an amorphous oxide semiconductor film contains, and it can be set as the film | membrane containing the area | region which oxygen content is excessive with respect to the stoichiometric composition ratio in an oxide semiconductor crystal state.

Therefore, the crystalline oxide semiconductor film formed is of high purity because impurities such as hydrogen and water are not mixed and oxygen is prevented from being released, and the content of oxygen is excessive with respect to the stoichiometric composition ratio in the oxide semiconductor. It can be set as a film containing a phosphorus region. Therefore, by using the crystalline oxide semiconductor film in the transistor 640, the variation in the threshold voltage Vth and the shift ΔVth of the threshold voltage due to the oxygen deficiency can be reduced.

As the insulating film 632, examples of the inorganic insulating material include an oxide insulating film such as a silicon oxide layer, a silicon oxynitride layer, an aluminum oxide layer, or an aluminum oxynitride layer, a silicon nitride layer, a silicon nitride oxide layer, an aluminum nitride layer, or an oxynitride. A single layer or lamination of a nitride insulating film such as an aluminum layer can be used.

As the interlayer insulating films 633 and 634, an insulating film that functions as a planarizing insulating film is preferable to reduce surface irregularities. As the interlayer insulating films 633 and 634, for example, organic insulating materials having heat resistance, such as polyimide, acrylic resin, benzocyclobutene resin, polyamide, and epoxy resin, can be used. In addition to the organic insulating material, a single layer or a laminate of a low dielectric constant material (low-k material), a siloxane resin, PSG (phosphorus glass), BPSG (phosphorus glass), or the like can be used.

By detecting the light incident on the photodiode 602, the information of the object to be detected can be read. In addition, a light source such as a backlight can be used when reading the information to be detected.

As described above, the transistor having a crystalline oxide semiconductor film which is highly purified and contains excessive oxygen to compensate for the oxygen deficiency is suppressed in fluctuation in electrical characteristics of the transistor and is electrically stable. Therefore, by using the transistor, a highly reliable semiconductor device can be provided.

This embodiment can be implemented in appropriate combination with any of the structures described in the other embodiments.

(Embodiment 13)

The transistor which shows an example in any one of Embodiment 1-10 can be used suitably for the semiconductor device which has an integrated circuit which laminated | stacks several transistors. In this embodiment, an example of a storage medium (memory element) is shown as an example of a semiconductor device.

In the embodiment, there is provided a semiconductor device including a transistor 140 which is a first transistor fabricated on a single crystal semiconductor substrate and a transistor 162 which is a second transistor fabricated using a semiconductor film above the transistor 140 via an insulating film. To make. The transistor shown in one of the embodiments 1 to 10 can be suitably used for the transistor 162. In this embodiment, an example in which a transistor having the same structure as that of the transistor 440 shown in the fifth embodiment is used as the transistor 162.

The semiconductor material and the structure of the transistor 140 and the transistor 162 to be stacked may be the same or different. In this embodiment, transistors of a material and a structure suitable for a circuit of a storage medium (memory element) are used respectively.

12 is an example of the configuration of a semiconductor device. 12A shows a cross section of the semiconductor device, and FIG. 12B shows a plane of the semiconductor device. Here, FIG. 12A is corresponded to the cross section in C1-C2 and D1-D2 of FIG. 12B. 12C shows an example of a circuit diagram when the semiconductor device is used as a memory element. The semiconductor device shown in FIGS. 12A and 12B has a transistor 140 using a first semiconductor material at the bottom and a transistor 162 using a second semiconductor material at the top. In this embodiment, the first semiconductor material is a semiconductor material other than an oxide semiconductor, and the second semiconductor material is an oxide semiconductor. As a semiconductor material other than an oxide semiconductor, silicon, germanium, silicon germanium, silicon carbide, gallium arsenide, etc. can be used, for example, It is preferable to use a single crystal semiconductor. In addition, you may use an organic semiconductor material. The transistor using such a semiconductor material is easy to operate at high speed. On the other hand, a transistor using an oxide semiconductor enables long-term charge retention due to its characteristics.

The manufacturing method of the semiconductor device in FIG. 12 is demonstrated using FIGS. 12A-12C.

The transistor 140 includes a channel forming region 116 formed in a substrate 185 containing a semiconductor material (for example, silicon, etc.) and an impurity region 120 formed between the channel forming region 116. And a metal compound region 124 in contact with the impurity region 120, a gate insulating film 108 formed on the channel formation region 116, and a gate electrode 110 formed on the gate insulating film 108.

As the substrate 185 containing the semiconductor material, a single crystal semiconductor substrate such as silicon or silicon carbide, a polycrystalline semiconductor substrate, a compound semiconductor substrate such as silicon germanium, an SOI substrate, or the like can be used. In addition, although a "SOI substrate" generally refers to the board | substrate of the structure in which the silicon semiconductor film was formed on the insulating surface, in this specification etc., the board | substrate of the structure in which the semiconductor film which consists of materials other than silicon was formed on the insulating surface is also included. That is, the semiconductor film which a "SOI substrate" has is not limited to a silicon semiconductor film. In addition, the SOI substrate is intended to include one having a structure in which a semiconductor film is formed over an insulating substrate such as a glass substrate via an insulating film.

As a method for producing an SOI substrate, by injecting oxygen ions into a mirror polished wafer, and then heating at a high temperature, an oxide layer is formed at a constant depth from the surface, and a defect generated in the surface layer is eliminated. The method of cleaving a semiconductor substrate using growth by the heat processing of a void, the method of forming a single crystal semiconductor film by crystal growth on an insulating surface, etc. can be used.

For example, ions are added from one side of the single crystal semiconductor substrate, a weakening layer is formed at a constant depth from one side of the single crystal semiconductor substrate, and either one side of the single crystal semiconductor substrate or on the element substrate An insulating film is formed in the film. In the state where the single crystal semiconductor substrate and the element substrate are overlapped with an insulating film interposed therebetween, cracks are generated in the weakened layer and heat treatment is performed to separate the single crystal semiconductor substrate from the weakened layer, thereby forming the single crystal semiconductor film as the semiconductor film from the single crystal semiconductor substrate. It is formed on the substrate. SOI substrates produced using the above method can also be suitably used.

An isolation layer 106 is formed on the substrate 185 to surround the transistor 140. In addition, in order to realize high integration, as shown in FIG. 12, it is preferable to set it as the structure which the transistor 140 does not have the side wall insulating layer used as a side wall. On the other hand, when importance is placed on the characteristics of the transistor 140, a sidewall insulating layer serving as a sidewall may be formed on the side surface of the gate electrode 110, and an impurity region 120 including regions having different impurity concentrations may be formed. .

The transistor 140 using the single crystal semiconductor substrate can operate at high speed. For this reason, reading of information can be performed at high speed by using the said transistor as a read transistor. Two insulating films are formed to cover the transistor 140. As a process before the formation of the transistor 162 and the capacitor 164, a CMP process is applied to the two layers of the insulating film, and the planarized insulating film 128 and the insulating film 130 are formed, and at the same time, the top surface of the gate electrode 110 is formed. Expose

The insulating film 128 and the insulating film 130 are typically a silicon oxide film, a silicon oxynitride film, an aluminum oxide film, an aluminum oxynitride film, a silicon nitride film, an aluminum nitride film, a silicon nitride oxide film, an aluminum nitride oxide film, or the like. The inorganic insulating film of can be used. The insulating film 128 and the insulating film 130 can be formed using a plasma CVD method, a sputtering method, or the like.

Moreover, organic materials, such as a polyimide, an acrylic resin, a benzocyclobutene type resin, can be used. In addition to the above organic materials, low dielectric constant materials (low-k materials) and the like can be used. When using an organic material, you may form the insulating film 128 and the insulating film 130 by wet methods, such as a spin coat method and the printing method.

In the insulating film 130, a silicon oxide film is used as the film in contact with the semiconductor film.

In this embodiment, a silicon oxynitride film having a thickness of 50 nm is formed by the sputtering method as the insulating film 128, and a silicon oxide film having a thickness of 550 nm is formed by the sputtering method as the insulating film 130.

A semiconductor film is formed on the insulating film 130 sufficiently flattened by the CMP process. In the present embodiment, an amorphous oxide semiconductor including a region in which the content of oxygen is excessive with respect to the stoichiometric composition ratio in the crystalline state of the oxide semiconductor by the sputtering method using an In—Ga—Zn-based oxide target as the semiconductor film. To form a film.

Next, the amorphous oxide semiconductor film is selectively etched to form an island-shaped amorphous oxide semiconductor film, and an oxygen introduction step is performed to the amorphous oxide semiconductor film. The gate insulating film 146, the gate electrode layer 148, and the sidewall insulating layers 136a and 136b are formed on the amorphous oxide semiconductor film.

As the gate insulating film 146, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon nitride oxide film, an aluminum oxide film, an aluminum nitride film, an aluminum oxynitride film, or an oxynitride using plasma CVD or sputtering An aluminum film, a hafnium oxide film, or a gallium oxide film can be formed.

The gate electrode layer 148 can be formed by selectively etching the conductive layer after forming the conductive layer on the gate insulating film 146.

Next, a conductive layer is formed over the gate electrode 110, the insulating film 128, the insulating film 130, and the like, and the conductive layer is selectively etched to form a source electrode or a drain electrode 142a, a source electrode or a drain electrode ( 142b).

The conductive layer can be formed using a PVD method including a sputtering method or a CVD method such as a plasma CVD method. As the material of the conductive layer, an element selected from Al, Cr, Cu, Ta, Ti, Mo, W, an alloy containing the above element as a component, and the like can be used. You may use any of Mn, Mg, Zr, Be, Nd, Sc, or the material which combined two or more.

The conductive layer may have a single layer structure or a laminate structure of two or more layers. For example, a single layer structure of a titanium film or a titanium nitride film, a single layer structure of an aluminum film containing silicon, a two-layer structure in which a titanium film is laminated on an aluminum film, a two-layer structure in which a titanium film is laminated on a titanium nitride film, a titanium film and an aluminum film And a three-layer structure in which a titanium film is laminated. In addition, in the case where the conductive layer has a single layer structure of a titanium film or a titanium nitride film, there is an advantage that processing into the source electrode or drain electrode 142a having a tapered shape and the source electrode or drain electrode 142b is easy. have.

Next, an insulating film 150 including an aluminum oxide film is formed over the amorphous oxide semiconductor film, the gate insulating film 146, the gate electrode layer 148, and the sidewall insulating layers 136a and 136b. In the case where the insulating film 150 has a laminated structure, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon nitride oxide film, an aluminum nitride film, an aluminum oxynitride film, or an oxynitride is formed by using a plasma CVD method or a sputtering method. An aluminum film, a hafnium oxide film, or a gallium oxide film may be formed by laminating with an aluminum oxide film.

Next, an amorphous oxide semiconductor film is subjected to heat treatment to crystallize at least a portion of the amorphous oxide semiconductor film to form a crystalline oxide semiconductor film 144 including crystals having a c-axis approximately perpendicular to the surface.

The aluminum oxide film formed as the insulating film 150 on the oxide semiconductor film has a high blocking effect (block effect) in which the film does not pass through both impurities such as hydrogen and moisture and oxygen.

Therefore, the aluminum oxide film prevents the incorporation of impurities, such as hydrogen and moisture, into the oxide semiconductor film during the production process and after the production, and the release of oxygen from the oxide semiconductor film as the main component material constituting the oxide semiconductor. It functions as a protective film to prevent.

Since the heat treatment for crystallizing the amorphous oxide semiconductor film is performed in a state covered with the aluminum oxide film formed as the insulating film 150, it is possible to prevent oxygen from being released from the amorphous oxide semiconductor film by the heat treatment for crystallization. Therefore, the obtained crystalline oxide semiconductor film 144 maintains the amount of oxygen contained in the amorphous oxide semiconductor film, so that the oxide semiconductor is a film containing an excess oxygen content with respect to the stoichiometric composition ratio in the crystal state. Can be.

Therefore, the crystalline oxide semiconductor film 144 formed is of high purity because impurities such as hydrogen and moisture are not mixed, and oxygen is prevented from being released, so that the oxide semiconductor has a ratio of oxygen to the stoichiometric composition ratio in the crystal state. It contains the region whose content is excess. Therefore, by using the crystalline oxide semiconductor film 144 in the transistor 162, the variation of the threshold voltage Vth and the shift ΔVth of the threshold voltage due to the oxygen deficiency can be reduced.

The temperature of the heat treatment for crystallizing at least a part of the amorphous oxide semiconductor film is 250 ° C or more and 700 ° C or less, preferably 400 ° C or more, more preferably 500 ° C, even more preferably 550 ° C or more.

On the insulating film 150, the electrode layer 153 is formed in an area overlapping the source electrode or the drain electrode 142a.

Next, an insulating film 152 is formed over the transistor 162 and the insulating film 150. The insulating film 152 can be formed using a sputtering method, a CVD method, or the like. It can also be formed using a material containing an inorganic insulating material such as silicon oxide, silicon oxynitride, silicon nitride, hafnium oxide or aluminum oxide.

Next, openings reaching the source electrode or the drain electrode 142b are formed in the gate insulating film 146, the insulating film 150, and the insulating film 152. The opening is formed by selective etching using a mask or the like.

Thereafter, a wiring 156 is formed in the opening in contact with the source electrode or the drain electrode 142b. In addition, the connection location of the source electrode or the drain electrode 142b and the wiring 156 is not shown in FIG.

The wiring 156 is formed by forming a conductive layer using a CVD method such as a PVD method or a plasma CVD method, including a sputtering method, and then etching the conductive layer. As the material of the conductive layer, an element selected from Al, Cr, Cu, Ta, Ti, Mo, W, an alloy containing the above element as a component, and the like can be used. You may use any of Mn, Mg, Zr, Be, Nd, Sc, or the material which combined multiple. The details are the same as the source electrode or the drain electrode 142a.

Through the above steps, the transistor 162 and the capacitor 164 are completed. The transistor 162 is a transistor having a crystalline oxide semiconductor film 144 that is highly purified and contains an excess of oxygen to compensate for oxygen deficiency. Therefore, the transistor 162 is suppressed from fluctuation in electrical characteristics and is electrically stable. The capacitor 164 is composed of a source electrode or a drain electrode 142a, a crystalline oxide semiconductor film 144, a gate insulating film 146, and an electrode layer 153.

In the capacitor 164 of FIG. 12, the crystalline oxide semiconductor film 144 and the gate insulating film 146 are stacked to ensure sufficient insulation between the source electrode or the drain electrode 142a and the electrode layer 153. can do. Of course, in order to ensure sufficient capacity, the capacitor 164 of the structure which does not have the crystalline oxide semiconductor film 144 may be employ | adopted. In addition, the capacitor 164 having the insulating film may be employed. In addition, when the capacitance is unnecessary, it is also possible to have a configuration in which the capacitor 164 is not formed.

12C shows an example of a circuit diagram when using the semiconductor device as a memory element. In FIG. 12C, one of the source electrode or the drain electrode of the transistor 162, one of the electrodes of the capacitor 164, and the gate electrode of the transistor 140 are electrically connected. The first wiring (also referred to as a source line) and the source electrode of the transistor 140 are electrically connected, and the second wiring (also referred to as a 2nd line: bit line) and the drain electrode of the transistor 140 are connected to each other. Is electrically connected. The third wiring (also referred to as a first signal line) and the other of the source electrode or the drain electrode of the transistor 162 are electrically connected, and the fourth wiring (also referred to as a second signal line) and The gate electrode of the transistor 162 is electrically connected. The fifth wiring (also called a word line) and the other of the electrode of the capacitor 164 are electrically connected.

Since the transistor 162 using the oxide semiconductor has a characteristic that the off current is very small, by turning off the transistor 162, one of the source electrode and the drain electrode of the transistor 162 and the capacitor 164 are provided. It is possible to maintain the potential of the node (hereinafter referred to as node FG) to which one of the electrodes of the electrode and the gate electrode of the transistor 140 are electrically connected for a very long time. By having the capacitor 164, the charge given to the node FG becomes easy, and the held information can be easily read.

When storing information (writing) in the semiconductor device, first, the potential of the fourth wiring is set to the potential at which the transistor 162 is turned on, and the transistor 162 is turned on. As a result, the potential of the third wiring is supplied to the node FG, and a predetermined amount of charge is accumulated in the node FG. Here, any one of charges (hereinafter, referred to as low level charges and high level charges) giving two different potential levels is given. After that, since the potential of the fourth wiring is set to the potential at which the transistor 162 is turned off and the transistor 162 is turned off, the node FG is left in a floating state, so that a predetermined charge is maintained at the node FG. It remains as it is. As described above, information can be stored in the memory cell by accumulating and retaining a predetermined amount of charges in the node FG.

Since the off current of the transistor 162 is very small, the charge supplied to the node FG is maintained for a long time. Therefore, the refresh operation becomes unnecessary, or the frequency of the refresh operation can be made very low, and the power consumption can be sufficiently reduced. In addition, even in the absence of power supply, it is possible to retain the stored contents for a long time.

When reading the stored information (reading), if a suitable potential (reading potential) is given to the fifth wiring in a state where a predetermined potential (static potential) is given to the first wiring, according to the amount of charge held in the node FG, Transistor 140 takes a different state. In general, when the transistor 140 is an n-channel type, the apparent threshold value V th _ H of the transistor 140 when the high level charge is held at the node FG is maintained at the low level charge at the node FG. This is because it becomes lower than the apparent threshold value V th _ L of the transistor 140 in the case where it is. Here, an apparent threshold value means the electric potential of the 5th wiring required in order to make transistor 140 "on state." Therefore, it is possible to determine the electric charge held in the node FG by the potential of the fifth wiring to a potential (V 0) between V th and V th _H _L. For example, when high level charge is given in writing, when the potential of the fifth wiring reaches V 0 (> V th_H ), the transistor 140 is in an "on state". When the low level charge is given, even when the potential of the fifth wiring becomes V 0 (<V th _ L), the transistor 140 remains in the “off state”. For this reason, the stored information can be read by controlling the potential of the fifth wiring to read the on state or the off state of the transistor 140 (reading the potential of the second wiring).

In the case where the stored information is rewritten, the new potential is supplied to the node FG in which the predetermined amount of charges is retained by the above-described recording, thereby maintaining the charge in accordance with the new information in the node FG. Specifically, the potential of the fourth wiring is set to the potential at which the transistor 162 is turned on, and the transistor 162 is turned on. As a result, the potential (potential according to the new information) of the third wiring is supplied to the node FG, and a predetermined amount of charge is accumulated in the node FG. Thereafter, the potential of the fourth wiring is set to the potential at which the transistor 162 is turned off and the transistor 162 is turned off, whereby the charge according to the new information is maintained at the node FG. That is, it is possible to overwrite the stored information by performing the same operation (second recording) as the first recording in the state where the predetermined amount of charge is held in the node FG by the first recording.

The transistor 162 shown in the present embodiment is highly purified, and the off current of the transistor 162 can be sufficiently reduced by using the oxide semiconductor film containing oxygen in the crystalline oxide semiconductor film 144. By using such a transistor, a semiconductor device capable of retaining the stored contents for a very long time is obtained.

As described above, the transistor having a crystalline oxide semiconductor film which is highly purified and contains excessive oxygen to compensate for the oxygen deficiency is suppressed in fluctuation in electrical characteristics of the transistor and is electrically stable. Therefore, by using the transistor, a highly reliable semiconductor device can be provided.

As mentioned above, the structure, method, etc. which are shown in this embodiment can be used in appropriate combination with the structure, method, etc. which are shown in another embodiment.

(Embodiment 14)

The semiconductor device disclosed in this specification can be applied to various electronic devices (including game machines). As the electronic apparatus, for example, a television device (also called a television or a television receiver), a monitor for a computer, a camera such as a digital camera, a digital video camera, a digital photo frame, a mobile phone (also referred to as a mobile phone or a mobile phone device). And a large game machine such as a portable game machine, a portable information terminal, an audio reproducing apparatus, and a pachining machine. An example of an electronic apparatus including the semiconductor device described in the above embodiment will be described.

FIG. 16A is a notebook PC, and is composed of a main body 3001, a housing 3002, a display portion 3003, a keyboard 3004, and the like. By applying the semiconductor device described in any one of Embodiments 1 to 13 to the display portion 3003, a highly reliable notebook PC can be obtained.

16B is a portable information terminal (PDA), in which a display portion 3023, an external interface 3025, an operation button 3024, and the like are formed in the main body 3021. There is also a stylus 3022 as an accessory for operation. By applying the semiconductor device described in any one of Embodiments 1 to 13 to the display unit 3023, a more reliable portable information terminal PDA can be obtained.

16C illustrates an example of an electronic book. For example, the electronic book is composed of two housings, a housing 2701 and a housing 2703. The housing 2701 and the housing 2703 are integrated by the shaft portion 2711, and the opening and closing operation can be performed with the shaft portion 2711 as the shaft. This configuration makes it possible to perform operations similar to books on paper.

The display portion 2705 is built in the housing 2701, and the display portion 2707 is built in the housing 2703. The display unit 2705 and the display unit 2707 may be configured to display a continuous screen or may be configured to display different screens. By setting the structure to display different screens, for example, sentences can be displayed on the right display unit (display unit 2705 in Fig. 16C), and images can be displayed on the left display unit (display unit 2707 in Fig. 16C). By applying the semiconductor device described in any one of Embodiments 1 to 13 to the display portion 2705 and the display portion 2707, a highly reliable electronic book can be obtained. When the transflective or reflective liquid crystal display device is used as the display portion 2705, use in a relatively bright situation is also expected, so that a solar cell can be installed, power generation by the solar cell, and charging with a battery can be performed. You may do so. In addition, the use of a lithium ion battery as a battery has advantages such as miniaturization.

In addition, in FIG. 16C, the housing 2701 is equipped with the operation part etc. are shown. For example, the housing 2701 includes a power supply 2721, an operation key 2723, a speaker 2725, and the like. The page can be turned by the operation key 2723. In addition, it is good also as a structure provided with a keyboard, a pointing device, etc. on the same surface as the display part of a housing. In addition, it is good also as a structure provided with the external connection terminal (earphone terminal, a USB terminal, etc.), a recording medium insertion part, etc. in the back surface or side surface of a housing. The electronic book may be configured to have a function as an electronic dictionary.

The electronic book may be configured to transmit and receive information wirelessly. It is also possible to make the structure which purchases and downloads desired book data etc. from an electronic book server by radio.

FIG. 16D is a mobile telephone and is composed of two housings, a housing 2800 and a housing 2801. The housing 2801 includes a display panel 2802, a speaker 2803, a microphone 2804, a pointing device 2806, a camera lens 2807, an external connection terminal 2808, and the like. The housing 2800 includes a solar cell 2810, an external memory slot 2811, and the like for charging a mobile phone. In addition, the antenna is embedded in the housing 2801. By applying the semiconductor device described in any one of Embodiments 1 to 13 to the display panel 2802, a highly reliable mobile phone can be obtained.

In addition, the display panel 2802 has a touch panel, and a plurality of operation keys 2805 displayed by video are shown by dotted lines in FIG. 16D. In addition, a booster circuit for boosting the voltage output from the solar cell 2810 to a voltage required for each circuit is also mounted.

In the display panel 2802, the direction of display is appropriately changed depending on the use form. In addition, since the camera lens 2807 is provided on the same plane as the display panel 2802, video telephony is possible. The speaker 1803 and the microphone 2804 are not limited to voice calls, and video calls, recording, and playback are possible. In addition, the housing 2800 and the housing 2801 can slide to be in an overlapped state in the unfolded state as shown in Fig. 16D, and can be miniaturized for portable use.

The external connection terminal 2808 can be connected to various cables such as an AC adapter and a USB cable, and can perform charging and data communication with a PC or the like. In addition, a recording medium can be inserted into the external memory slot 2811 to cope with a larger amount of data storage and movement.

In addition to the above functions, an infrared communication function, a television reception function, or the like may be provided.

FIG. 16E is a digital video camera and is composed of a main body 3051, a display portion (A) 3057, an eyepiece portion 3053, an operation switch 3054, a display portion (B) 3055, a battery 3056, and the like. . By applying the semiconductor device described in any one of Embodiments 1 to 13 to the display portion (A) 3057 and the display portion (B) 3055, a highly reliable digital video camera can be obtained.

16F shows an example of a television device. In the television apparatus, the display portion 9603 is incorporated in the housing 9601. The display portion 9603 can display an image. In addition, the structure which supported the housing 9601 by the stand 9605 is shown here. By applying the semiconductor device described in any one of Embodiments 1 to 13 to the display portion 9603, a highly reliable television device can be obtained.

The operation of the television device can be performed by an operation switch included in the housing 9601 or a separate remote controller. In addition, it is good also as a structure which forms the display part which displays the information output from the said remote controller in a remote controller.

In addition, a television device is provided with a receiver, a modem, or the like. General television broadcasting can be received by the receiver, and by connecting to a communication network by wire or wireless via a modem, information in one direction (from sender to receiver) or in two directions (between sender and receiver, or between receivers, etc.) It is also possible to communicate.

This embodiment can be implemented in appropriate combination with any of the structures described in the other embodiments.

(Example)

In this embodiment, evaluation was made as to the characteristics of the aluminum oxide film used as the barrier film in the semiconductor device according to the disclosed invention. The results are shown in FIGS. 17 to 20. As an evaluation method, secondary ion mass spectrometry (SIMS) and thermal desorption spectroscopy (TDS) analysis were used.

First, evaluation performed by SIMS analysis is shown. As a comparative example, a silicon oxide film having a thickness of 100 nm was formed on a glass substrate by a sputtering method on a glass substrate as a comparative example, and a silicon oxide film having a thickness of 100 nm was formed on a glass substrate by a sputtering method on a glass substrate, and sputtered on a silicon oxide film. Example Sample A in which an aluminum oxide film was formed to a thickness of 100 nm by the method was produced.

In Comparative Example Sample A and Example Sample A, the silicon oxide film deposition conditions used a silicon oxide (SiO 2 ) target as a target, and the distance between the glass substrate and the target was 60 mm, pressure 0.4 Pa, power supply 1.5 kW, The substrate temperature was set at 100 ° C. under an oxygen (oxygen flow rate of 50 sccm) atmosphere.

Example In the sample A, the aluminum oxide film formation conditions are, as a target of aluminum oxide (Al 2 O 3), and using the target, the 60mm distance between the glass substrate and the target, pressure 0.4Pa, power supply 1.5kW, argon and oxygen (Argon flow rate 25 sccm: Oxygen flow rate 25 sccm) The substrate temperature was 250 degreeC in atmosphere.

A pressure cooker test (PCT: Pressure Cooker Test) was performed on Comparative Sample A and Example Sample A. In the present Example, as a PCT test, Comparative Example Sample A and the implementation were carried out under conditions of a temperature of 130 ° C., a humidity of 85%, H 2 O (water): D 2 O (heavy water) = 3: 1 atmosphere, and 2.3 atmosphere (0.23 MPa). Example Sample A was held for 100 hours.

As the SIMS analysis, the concentration of H atoms and D (deuterium) atoms of each sample was measured for Comparative Example Sample A and Example Sample A before and after the PCT test using SSDP (Substrate Side Depth Profile) -SIMS. Also, D is the atom, one of the hydrogen isotope, it expressed as elemental symbols and H 2.

17A1 shows the concentration profiles of H atoms and D atoms by SIMS before the PCT test of Comparative Example Sample A and after the PCT test of Comparative Example Sample A in FIG. 17A2. 17A1 and 17A2, the D atom expected profile is a concentration profile of D atoms present in the natural system calculated from the profile of H atoms with an abundance ratio of D atoms of 0.015%. Therefore, the amount of D atoms mixed in the sample by the PCT test is a difference between the measured D atom concentration and the D atom expected concentration. The concentration profile of D atom minus D atom expected concentration by the measured D atom concentration is shown in FIG. 17B1 before the PCT test and FIG. 17B2 after the PCT test.

Similarly, FIG. 18A1 shows the concentration profiles of H atoms and D atoms by SIMS before the PCT test of Example Sample A and after the PCT test of Example Sample A in FIG. 18A2. In addition, FIG. 18B1 shows the concentration profile of the D atom obtained by subtracting the D atom expected concentration from the measured D atom concentration, before and after the PCT test, and FIG. 18B2 after the PCT test.

In addition, the SIMS analysis result of this Example has shown the result quantified all by the standard sample of a silicon oxide film.

As shown in Fig. 17, the concentration profile of the measured D atoms and the expected D atom profiles overlapped before the PCT test, and the concentration profile of the measured D atoms after the PCT test are increased to a high concentration. It can be seen that the atoms are mixed. Therefore, it was confirmed that the silicon oxide film of the comparative example sample was low in barrier property to moisture (H 2 O, D 2 O) from the outside.

On the other hand, as shown in Fig. 18, in Example Sample A in which an aluminum oxide film was laminated on a silicon oxide film, D atoms only slightly appeared on the surface of the aluminum oxide film even after the PCT test. And intrusion of D atoms does not appear in the silicon oxide film. Therefore, it was confirmed that the aluminum oxide film had a high barrier property against moisture (H 2 O, D 2 O) from the outside.

Next, the evaluation performed by TDS analysis is shown. The sample produced the Example sample B in which the silicon oxide film | membrane 100 nm in thickness was formed on the glass substrate by the sputtering method, and the aluminum oxide film 20 nm in thickness was formed on the silicon oxide film by the sputtering method. In addition, as a comparative example, after measuring the sample sample B by TDS analysis, the aluminum oxide film was removed from the sample sample B, and the comparative sample sample B in which only the silicon oxide film was formed on the glass substrate was produced.

In Comparative Example Sample B and Example Sample B, the silicon oxide film deposition conditions were a silicon oxide (SiO 2 ) target as a target, and the distance between the glass substrate and the target was 60 mm, pressure 0.4 Pa, power supply 1.5 kW, The substrate temperature was set at 100 ° C. under an oxygen (oxygen flow rate of 50 sccm) atmosphere.

EXAMPLES In sample B, the film forming conditions of the aluminum oxide film were aluminum aluminum (Al 2 O 3 ) targets as targets, and the distance between the glass substrate and the targets was 60 mm, pressure 0.4 Pa, power supply 1.5 kW, argon and oxygen. (Argon flow rate 25 sccm: Oxygen flow rate 25 sccm) The substrate temperature was 250 degreeC in atmosphere.

In Comparative Example Sample B and Example Sample B, each sample was further treated under nitrogen atmosphere for 1 hour under conditions of 300 ° C. heat treatment, 450 ° C. heat treatment, and 600 ° C. heat treatment.

In Comparative Example Sample B and Example Sample B, TDS analysis was performed on the samples produced without heating treatment, 300 캜 heating treatment, 450 캜 heating treatment, 600 캜 heating treatment and four conditions, respectively. In Comparative Example Sample B and Example Sample B, there was no heat treatment in FIGS. 19A and 20A, 300 ° C heat treatment in FIGS. 19B and 20B, 450 ° C heat treatment in FIGS. 19C and 20C, and FIGS. 19D and 20D. subjected to heat treatment 600 ℃ shows the results of the TDS M / z = 32 (O 2 ) measurement of the samples.

As shown in Figs. 19A to 19D, in Comparative Example Sample B, oxygen was released from the silicon oxide film in Fig. 19A without heat treatment, but in the sample subjected to the 300 ° C heat treatment in Fig. 19B, the amount of oxygen released was greatly reduced. In addition, in the sample which performed the 450 degreeC heat processing of FIG. 19C, and the sample which performed the 600 degreeC heat processing of FIG. 19D, it became below the background of TDS measurement.

19A to 19D show that at least 90% of the excess oxygen contained in the silicon oxide film is released to the outside in the silicon oxide film by the heat treatment at 300 ° C, and by the heat treatment at 450 ° C and 600 ° C. It can be seen that excess oxygen contained in almost all the silicon oxide films was released to the outside of the silicon oxide film. Therefore, it was confirmed that the silicon oxide film had a low barrier property against oxygen.

On the other hand, in Example Sample B in which an aluminum oxide film was formed on a silicon oxide film, as shown in Figs. 20A to 20D, even in a sample subjected to heat treatment at 300 ° C, 450 ° C, and 600 ° C, no heat treatment was performed. Emission of the same amount of oxygen as the sample was observed.

20A to 20D show that the aluminum oxide film is formed on the silicon oxide film so that the excess oxygen contained in the silicon oxide film is not easily released to the outside even when the heat treatment is performed. It can be seen that it is maintained to a considerable extent. Therefore, it was confirmed that the aluminum oxide film had a high barrier property against oxygen.

From the above results, it was confirmed that the aluminum oxide film has both a barrier property against hydrogen and moisture and a barrier property against oxygen, and functions suitably as a barrier film against hydrogen, water and oxygen.

Therefore, the aluminum oxide film is mixed with impurities such as hydrogen, moisture, and the like as oxide components in the oxide semiconductor film during the fabrication process and after fabrication of the transistor including the oxide semiconductor film, and oxygen as the main component material constituting the oxide semiconductor. It can function as a protective film which prevents the emission from the oxide semiconductor film.

Therefore, the crystalline oxide semiconductor film formed is of high purity because impurities such as hydrogen and moisture are not mixed, and oxygen content is excessive with respect to the stoichiometric composition ratio of the oxide semiconductor in the crystal state because oxygen release is prevented. It includes an area. Therefore, by using the crystalline oxide semiconductor film in the transistor, the variation in the threshold voltage Vth and the shift ΔVth of the threshold voltage due to the oxygen deficiency can be reduced.

106; Device isolation insulating layer 108; Gate insulating film
110; Gate electrode 116; Channel formation area
120; Impurity region 124; Metal compound zone
128; Insulating film 130; Insulating film
136a; Sidewall insulation layer 136b; Sidewall insulation layer
140; Transistor 142a; Drain electrode
142b; Drain electrode 144; Crystalline oxide semiconductor film
146; A gate insulating film 148; Gate electrode layer
150; Insulating film 152; Insulating film
153; Electrode layer 156; Wiring
162; Transistor 164; Capacitive element
185; Substrate 400; Board
401; Gate electrode layer 402; Gate insulating film
403; Crystalline oxide semiconductor film 404a; Impurity region
404b; Impurity region 405a; Source electrode layer
405b; Drain electrode layer 407; Insulating film
407a; Insulating film 407b; Insulating film
410; Transistor 410a; transistor
412a; Sidewall insulating layer 412b; Sidewall insulation layer
415; Planarization insulating film 420; transistor
420a; Transistor 420b; transistor
430; Transistor 431; Oxygen
436; Insulating film 440; transistor
440a; Transistor 440b; transistor
441; Amorphous oxide semiconductor film 442; Gate insulating film
443; Amorphous oxide semiconductor film 444; Crystalline oxide semiconductor film
450; Transistor 450a; transistor
450b; Transistor 450c; transistor
491; Amorphous oxide semiconductor film 492; Amorphous oxide semiconductor film
601; Substrate 602; Photodiode
606a; Semiconductor film 606b; Semiconductor film
606c; Semiconductor film 608; Adhesive layer
613; Substrate 631; Insulating film
632; Insulating film 633; Interlayer insulation film
634; Interlayer insulating film 640; transistor
641; Electrode layer 642; Electrode layer
643; Conductive layer 645; Conductive layer
656; Transistor 658; Photodiode Reset Signal Line
659; Gate signal line 671; Photoelectric Sensor Output Signal Line
672; Photosensor reference signal line 2700; Electronic books
2701; Housing 2703; housing
2705; Display portion 2707; Display
2711; Shaft portion 2721; power
2723; Operation key 2725; speaker
2800; Housing 2801; housing
2802; Display panel 2803; speaker
2804; Microphone 2805; Operation keys
2806; Pointing device 2807; Lens for the camera
2808; External connection terminal 2810; Solar cell
2811; External memory slot 3001; main body
3002; Housing 3003; Display
3004; Keyboard 3021; main body
3022; Stylus 3023; Display
3024; Operation button 3025; External interface
3051; Body 3053; Eyepiece
3054; Operation switch 3056; battery
4001; Substrate 4002; Pixel part
4003; Signal line driver circuit 4004; Scanning line driving circuit
4005; Sealant 4006; Board
4008; Liquid crystal layer 4010; transistor
4011; Transistor 4013; Liquid crystal elements
4015; Connection terminal electrode 4016; Terminal electrode
4018; FPC 4019; Anisotropic conductive film
4020; Insulating film 4021; Insulating film
4023; Insulating film 4024; Insulating film
4030; Electrode layer 4031; Electrode layer
4032; Insulating film 4033; Insulating film
4510; Bulkhead 4511; Electroluminescent layer
4513; Light emitting element 4514; filling
9600; Television device 9601; housing
9603; Display portion 9605; stand

Claims (10)

delete In the semiconductor device manufacturing method,
Forming an insulating film;
Forming an amorphous oxide semiconductor film on the insulating film;
Performing a first heat treatment on the amorphous oxide semiconductor film under a reduced pressure or a nitrogen atmosphere;
Introducing oxygen into the amorphous oxide semiconductor film to form an amorphous oxide semiconductor film containing the introduced oxygen;
Forming an aluminum oxide film on the amorphous oxide semiconductor film containing the introduced oxygen; And
Performing a second heat treatment on the amorphous oxide semiconductor film containing the introduced oxygen to form an oxide semiconductor film containing crystals,
The first heat treatment is performed at a temperature of 400 ° C. or less,
The second heat treatment is performed at a temperature of 500 ° C. or higher,
And the oxygen is introduced into the amorphous oxide semiconductor film using an ion implantation method or an ion doping method. In the semiconductor device manufacturing method,
Forming an insulating film;
Forming an amorphous oxide semiconductor film on the insulating film;
Performing a first heat treatment on the amorphous oxide semiconductor film under a reduced pressure or a nitrogen atmosphere;
Forming an aluminum oxide film on the amorphous oxide semiconductor film;
Introducing oxygen into the amorphous oxide semiconductor film through the aluminum oxide film; And
Performing a second heat treatment on the amorphous oxide semiconductor film containing the introduced oxygen to form an oxide semiconductor film containing crystals,
The first heat treatment is performed at a temperature of 400 ° C. or less,
The second heat treatment is performed at a temperature of 500 ° C. or higher,
And the oxygen is introduced into the amorphous oxide semiconductor film using an ion implantation method or an ion doping method. The method of claim 2 or 3,
And said crystal contained in said oxide semiconductor film has a c-axis perpendicular to a surface thereof. The method of claim 2,
Forming a gate insulating film on the amorphous oxide semiconductor film after performing the first heat treatment,
And the oxygen is introduced into the amorphous oxide semiconductor film through the gate insulating film. The method of claim 2,
Forming a gate insulating film on the amorphous oxide semiconductor film after performing the first heat treatment; And
Forming a gate electrode layer on the gate insulating layer after introducing oxygen;
And the oxygen is introduced into the amorphous oxide semiconductor film through the gate insulating film. delete delete delete The method of claim 2 or 3,
And the amorphous oxide semiconductor film has a more uniform amorphous state by introducing the oxygen.
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